Received: 4 October 2019 Revised: 26 March 2020 Accepted: 31 March 2020

DOI: 10.1111/1541-4337.12566

COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY

Natural phenolic antioxidants electrochemistry: Towards a new

food science methodology

Ana-Maria Chiorcea-Paquim1 Teodor Adrian Enache1 Eric De Souza Gil1,2

Ana Maria Oliveira-Brett1

1 CEMMPRE, Department of Chemistry,

Abstract
University of Coimbra, Coimbra, 3004-535,
Portugal Natural phenolic compounds are abundant in the vegetable kingdom, occurring
2 Faculdadede Farmácia, Universidade mainly as secondary metabolites in a wide variety of chemical structures. Around
Federal de Goiás, Setor Universitário, 10,000 different plant phenolic derivatives have been isolated and identified. This
Goiânia, Goiás, Brasil
review provides an exhaustive overview concerning the electron transfer reactions
Correspondence in natural polyphenols, from the point of view of their in vitro antioxidant and/or
Ana Maria Oliveira-Brett, CEMMPRE,
pro-oxidant mode of action, as well as their identification in highly complex matrixes,
Department of Chemistry, University of Coim-
bra, Coimbra 3004-535, Portugal. for example, fruits, vegetables, wine, food supplements, relevant for food quality
Email: [email protected] control, nutrition, and health research. The accurate assessment of polyphenols’ redox
behavior is essential, and the application of the electrochemical methods in routine
Funding information
Fundação para a Ciência e a Tecnologia, quality control of natural products and foods, where the polyphenols antioxidant
Grant/Award Number: UID/EMS/00285/2013 activity needs to be quantified in vitro, is of the utmost importance. The phenol
moiety oxidation pathways and the effect of substituents and experimental conditions
on their electrochemical behavior will be reviewed. The fundamental principles con-
cerning the redox behavior of natural polyphenols, specifically flavonoids and other
benzopyran derivatives, phenolic acids and ester derivatives, quinones, lignins, tan-
nins, lignans, essential oils, stilbenes, curcuminoids, and chalcones, will be described.
The final sections will focus on the electroanalysis of phenolic antioxidants in natural
products and the electroanalytical evaluation of in vitro total antioxidant capacity.

KEYWORDS
polyphenol, flavonoid, antioxidant, electrochemistry, voltammetry

1 I N T RO D U C T I O N such foods being used for thousands of years with therapeutic

benefit.
Natural phenolic compounds, also known as polyphenols, Simple and low-molecular weight phenolic monomers,
are ubiquitous in the vegetable kingdom, and occur in a as well as the substructures of the complex high molec-
wide variety of structures (Figure 1). They are essential for ular weight polyphenols (Figure 1) have different names
the growth and reproduction of plants, and are produced to depending on the number of phenolic hydroxyl (–OH)
defend injured plants against pathogens. They are secondary groups. The phenol structure has one phenolic –OH group;
metabolites of plants, and are known as hormones, vitamins, catechol, hydroquinone, and resorcinol (benzenediol) struc-
and food antioxidants. The presence of polyphenols in food tures have two phenolic –OH groups; and gallocatechol and
confers remarkable organoleptic characteristics, that is, color, phloroglucinol (benzenetriol) structures have three phenolic
flavor, and bitterness, and also has a great impact on health, –OH groups (Figure 2).

1680 © 2020 Institute of Food Technologists® wileyonlinelibrary.com/journal/crf3 Compr Rev Food Sci Food Saf. 2020;19:1680–1726.
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1681

O OH O
HO
OH OH

HO

COMPLEXITY AND MOLECULAR MASS

Phenolic acids
O
O O

O O O
Naphthoquinones Chromones Flavones

O
O O

OH
O O
Catechins Styrylchromones Anthraquinones

O OH

OH HO OH
OH
HO OH
O O
O O
O O
OH O O O
O
O
O OH
HO
HO O OH O
HO
HO O
O

O O
OH

Lignans HO
O OH
Lignins
F I G U R E 1 Complexity and molecular mass of some phenolic compounds found in plant foods

OH
Most polyphenols are formed by the deamination of the
phenylalanine and tyrosine amino acids to cinnamic acids,
as part of the phenylpropanoid pathway. Although these
Phenol, mono-phenol compounds have a common carbon C6-C3 phenylpropanoid
OH OH element, an essential step in their biosynthesis is the attach-
OH OH ment of one or more –OH groups to the phenyl ring, which
gives rise to a great diversity of molecules (Tsao, 2010):
HO OH cinnamic acids (C6-C3), benzoic acids (C6-C1), flavonoids
Catechol, di-phenol Hydroquinone, di-phenol Resorcinol, di-phenol (C6-C3-C6), proanthocyanidins [(C6-C3-C6)n], coumarins
OH OH
(C6-C3), stilbenes (C6-C2-C6), lignans (C6-C3-C3-C6), and
lignins [(C6-C3)n] (Figure 3). In fact, owing to their many
OH
complex structures, around 10,000 different plant phenolic
derivatives have already been isolated and identified.
OH HO OH
Phenolic compounds are recognized to have a large
Gallocatechol, tri-phenol Phloroglucinol, tri-phenol
variety of biological activities, such as antiallergic, anti-
F I G U R E 2 Phenol chemical structures inflammatory, antimutagenic, anticarcinogenic, and are
modulators of enzymatic activities, having pharmacological
actions against oxidative damage diseases, which include
1682 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

F I G U R E 3 Natural phenolic compounds

Flavones (luteolin, orientin) and
Flavonols (quercetin, rutin) classification and occurrence
onion, lettuce, red wine, etc.
Flavanones (eriodictyol, hesperetin) and
Flavanonols (taxifolin)
apples, citrus, etc.
Isoflavonoids (genistein, daidzein)
Flavonoids soy beans, fava beans
and other Flavanols (catechin, gallocatechin, epicatechin)
Benzopyran tea leaves, coffee, cacao beans, etc.
Derivatives Anthocyanidins (cyanidin, malvidin) and
Anthocyanins (glycosides of cyanidin, malvidin)
red fruits, red cabbage, etc.
NATURAL Chromones (eucryphin, cromolyn)
PHENOLIC barks of leguminous plants, etc.
Coumarins (coumarin, scopoletin, aesculetin)
COMPOUNDS tonka bean, vanilla grass, etc.
Xanthones (mangostin and mangiferin)
mangosteen, mangoes

Hydroxycinnamic Acids (caffeic, ferulic acids)

Phenolic Acids mushrooms, coffee, wine, etc.
Dietary and Ester Hydroxycinnamoyl Esters Derivatives (caftaric,
sources Derivatives
coutaric, rosmarinic acids, verbascoside)
aromatic plants, spices, etc.
Hydroxybenzoic Acids (salicylic, gallic acids)
berries, olives, green pepper, etc.

Naphthoquinones (lapachol, juglone, lawsone)

Quinones bark of the lapacho tree, fungi, etc.
Anthraquinones (emodin, rhein)
Fruits pigmentated plants, lichen, etc.

Vegetables Lignins (variable and non-defined polymeric structure)

humus, algae, all plants.
Grains
Tannins (tannic acid )
red wood bark, seaweeds, etc..
Lignans (pinoresinol, sesamol, cordigol, silybin)
phytoestrogens of a variety of plants
Essential Oils (guaiacol, syringol, eugenol, thymol, carvacrol)
aromatic plants
Stilbenes (resveratrol, pterostilbene, gnetol, piceatannol)
red wines, grapes, etc.
Curcuminoids (curcumin)
turmeric root
Chalcones (phloretin)
apple tree, Manchurian apricot

inflammatory disorders, coronary heart disease, strokes, can- pro-oxidant action, producing free radicals. However, this
cer, and age-related diseases. Their biomolecular mechanisms pro-oxidant activity may also be essential for the polyphenols’
of action have been studied (Patil & Masand, 2018), and may ability to work as antimicrobial, antipathogenic, therapeutic
include: antioxidant effects, by inactivation of reactive oxygen agents, and defense or deleterious agents, that is, apoptosis,
species (ROS), binding of electrophiles, induction of protec- in immunological defense mechanisms and aging processes.
tive enzymes, inhibition of lipid peroxidation, increasing the Such duality depends on the physiological conditions and on
apoptosis rate, inhibition of cellular proliferation, angiogene- the polyphenol chemical properties.
sis inhibition, H-donation, and inhibition of DNA oxidation. Electrochemical methods are widely used to characterize
The polyphenols’ in vivo structure–antioxidant capacity the redox properties of molecules, providing informa-
relationship is still not well understood, but the polyphenol tion about electron transfer reactions, with or without
in vitro antioxidant capacity is well established, being coupled chemical reactions, and their redox potentials.
closely related to their redox behavior and electron transfer They have also been associated with the use of elec-
reactions. Moreover, although polyphenols are commonly trochemical detectors (EC) in high-performance liquid
known for their antioxidant effects that contribute positively chromatography (HPLC) and flow injection analysis (FIA)
to the oxidative stress protection and balance, within certain systems, biosensor development, coulometer, and column
physiological conditions, they can also exert a dangerous electrolysis.
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1683

(a) (b)
Flavonoids
and other
Stilbenes, Fuels and
Benzopyran Others
Curcuminoids Lubricants
Derivatives
and Chalcones industry
Phenolic Acids Pharmaceutical
and Ester Plastic and industry
Essential Oils Derivatives rubber industry

Lignans
Quinones Cosmetic
Food
industry
Tannins Lignins industry

F I G U R E 4 Natural phenolic compounds: (a) classification and (b) applications

In fact, electroanalytical techniques are most suitable for The knowledge arising from the polyphenols’ electro-
the characterization of electroactive species and assessment of chemical evaluation represents an important parameter in
in vitro total antioxidant capacity (Macêdo et al., 2017). The the development of new accurate in vitro screening methods
continuous search for less expensive and fast analytical meth- for routine quality control, and for increased understanding
ods, established the importance of electrochemical methods concerning their safe use in diet regimes, food supple-
in the assessment of phenolic compounds’ in vitro antioxidant ments, and nutripharmaceuticals for disease prevention and
capacity, elucidation of their redox behavior mechanisms, treatment in healthcare (Tungmunnithum et al., 2018).
and their identification in matrices of high complexity, for
example, fruits, vegetables, wine, food supplements, and
pharmaceutical drugs (Cragg & Newman, 2005; Tung- 2 ELECTROCHEMICA L BEHAV IOR
munnithum, Thongboonyou, Pholboon, & Yangsabai, 2018). O F P H ENO LIC COM P O UNDS
Phenolic antioxidants are used in many applications,
including food, pharmaceuticals, cosmetics, plastic, rubber, The phenolic antioxidants’ electrochemical reactions have
fuel, lubricant, and so on (Figure 4), the global phenolic been investigated, and a relationship between their electron
antioxidant market being expected to reach USD 1.83 billion transfer properties and radical-scavenging activity has been
by 2023. The correct assessment of polyphenol electrochemi- found in many polyphenol groups, which include flavonoids
cal characteristics is essential for promoting the application of (quercetin, rutin, myrecetin, epigallocatechin), xanthonoids
electrochemical methods in routine quality control of natural (mangiferin, magostin), phenolic acids (chlorogenic acid,
products, foods, pharmaceutical drugs, and supplements, caffeic acid, ferullic acid), phenolic acid esters (verbascoside,
where the polyphenol antioxidant activity of commercial rosmarinic, ellagic acid), and anthraquinones (danthrone,
samples needs to be quantified in vitro (Granato et al., 2018). emodin, rhein). The inherent redox active phenol moiety,
This review aims to provide a comprehensive and exhaus- common to almost all these compounds, is what confers their
tive overview of the fundamental principles concerning the antioxidant properties.
electron transfer reactions in natural polyphenols from the The polyphenols’ chemical properties and in vitro
point of view of their antioxidant and/or pro-oxidant mode of antioxidant capacity also depend on the phenolic hydro-
action, relevant for food quality control, nutrition, and health gens, as hydrogen-donating radical scavengers, and can
research. be described by three main mechanisms: electron/proton
The first section revisits the phenol moiety oxidation path- donor properties of electroactive phenol moieties, metal
ways, and the effect of substituents and experimental condi- chelation properties of bidentate phenolic functions, and
tions on their electrochemical behavior. An overview of the binding interaction with biologically active proteins, that is,
fundamental principles concerning the electron transfer reac- oxireductases (Rice-Evans, Miller, & Paganga, 1996).
tions in natural polyphenols, specifically flavonoids and other A phenolic compound is defined as an antioxidant when,
benzopyran derivatives, phenolic acids and ester derivatives, present in low concentration relative to the substrate that will
quinones, lignins, tannins, lignans, essential oils, stilbenes, undergo oxidation, it delays, retards, or prevents autoxidation
curcuminoids, and chalcones, will then be described. The or free radical-mediated oxidation, the radical formed after
final sections are focused on the electroanalysis of phenolic scavenging being stable (Halliwell & Gutteridge, 2015).
antioxidants in natural products and the electroanalytical The phenolic antioxidant reaction mechanisms have been
evaluation of in vitro total antioxidant capacity. extensively studied by a number of analytical methods
1684 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

(Robbins, 2003), showing that their mechanism of action is

ortho-quinone para-quinone
associated with their capacity to scavenge free radicals, via group Polymeric film group
(a) hydrogen–atom transfer and/or proton–coupled electron
Reversible Reversible
transfer, (b) sequential electron transfer–proton transfer, two-electron- two-electron-
proton Irreversible
(c) sequential proton loss–electron transfer, and (d) adduct oxidation proton
step step
formation (Dangles, Dufour, Tonnelé, & Trouillas, 2016; Hydroquinone
Catechol group
Leopoldini, Russo, & Toscano, 2011). All mechanisms result group
in the formation of phenoxy radicals. Irreversible
one-electron-
The main electrochemical methods used to elucidate the proton
natural polyphenols’ redox behavior are cyclic voltammetry step

(CV), differential pulse voltammetry (DPV), and square

wave voltammetry (SWV), in stationary solution, and HPLC Phenol group
separation with electrochemical detection (HPLC–EC), in
flow analysis, (Arribas, Martínez-Fernández, & Chicharro, Irreversible
oxidation
2012; Magalhães, Ribeiro, Segundo, Reis, & Lima, 2009).
All polyphenols present a common redox behavior,
electrochemical oxidation occurring at the –OH groups, and Polymeric film
influenced by the chemical substituents linked to the aromatic
F I G U R E 5 Phenol moiety oxidation pathways
rings (e.g., –OCH3 , sugar, etc.). Among other factors, the pH
of the environment is the most important, directly affecting
the polyphenols’ antioxidant capacity, redox behavior, and ortho-quinone and para-quinone (Figure 6). Therefore, the
oxidation product formation (Rene, Abasq, Hauchard, & total reaction is an electron transfer reaction (E) followed by
Hapiot, 2010). a chemical reaction (C), an electrochemical–chemical (EC)
The natural polyphenols’ oxidation reactions can also mechanism, the hydrolysis only occurring at a high electrode
be followed by chemical reactions, in which the oxidation potential.
product and/or the dimers and polymers formed may be The phenol oxidation products formed at peak 1a are
electroactive and adsorb at the electrode surface. The unusu- reversibly reduced, the ortho-quinone to catechol (peak 3c)
ally large electron transfer numbers, found in polyphenols and the para-quinone to hydroquinone (peak 2c, Figures 6
oxidation, are in agreement with the electrogeneration of new and 7). The catechol and hydroquinone reversible electron
–OH moieties during oxidative polymerization. transfer mechanism occurs in two parallel processes with the
transfer of two electrons and two protons each.
Differential pulse voltammograms (DPVs) of phenol
2.1 Phenol moiety oxidation (Figure 7) show, in the first scan, that phenol oxidation is
Natural polyphenols present a great structural diversity and, pH-dependent, the width at half maximum height of peak 1a,
although their oxidation occurs at the same electroactive W1/2 ∼ 100 mV, corresponding to an irreversible one-electron
groups, predominantly occurring at the phenol moiety, it and one-proton transfer (Brett & Oliveira-Brett, 1993, 1998).
is not easy to describe their redox mechanism in detail. In the second scan, the oxidation peaks of the adsorbed
The main differences are due to the influence of the non- phenol oxidation products, peak 2a of ortho-quinone (cate-
electroactive substituents (Figure 5). The phenolic –OH chol), and peak 3a of para-quinone (hydroquinone), are also
moiety undergoes anodic oxidation according to the stability pH-dependent, W1/2 ∼ 60 mV corresponding to a reversible
of the electrogenerated phenoxy radical, which is dependent two-electron and two-proton transfer.
on phenol and phenolic substituents. Based on phenol oxidation, some basic principles that
The phenol moiety redox mechanism was studied at a might be applied to all phenolic compounds can be high-
glassy carbon electrode (GCE) (Enache & Oliveira-Brett, lighted (Arslan, Yazici, & Erbil, 2005; Nasr et al., 2005;
2011b), and the natural phenol antioxidant activity clarified. Yamamura, 2003):
The CV results showed that phenol oxidation occurs with the
transfer of one electron and one proton (peak 1a, Figure 6). 1. Phenol is oxidized, in one-electron, one-proton irreversible
Phenol is oxidized to a phenoxy radical that is thermody- step, to a phenoxy radical.
namically unstable and coexists in three resonant forms (A at 2. As in homogeneous reactions, the activation energy of
ortho- and B at para- positions with higher spin density, and heterogeneous electrochemical reactions is driven by the
the meta- position with lower spin density), being stabilized stability of the intermediates. Therefore, in the case of
by hydrolysis at a high applied potential (anodic peak 1a), phenol anodic oxidation, it depends on the stability of the
resulting in the formation of two electroactive products, electrogenerated phenoxy radical.
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1685

F I G U R E 6 Cyclic voltammograms (CVs) at a GCE, in 30 μM phenol in pH 7.0: (▬) first and (•••) second scans, 𝜈 = 50 mV/s, and phenol
oxidation mechanism. Adapted from (Enache & Oliveira-Brett, 2011b) with permission

F I G U R E 7 3D plots of DPVs with baseline

1 scan 1a
subtracted at a GCE, 𝜈 = 5 mV/s, in 25 μM phenol, 2 scan
first and second scans. Adapted from (Enache &
Oliveira-Brett, 2011b) with permission 2a 3a
20 nA

20 nA 10
10 8
8 6
6
4 pH 4 pH
2 -0.2 0.0 0.2 2
0.2 0.4 0 0.4 0.6 0.8 0
0.6 0.8 1.0 1.2 1.0 1.2
E/V vs. Ag
E/V vs. Ag/AgCl /AgCl

3. The unstable phenoxy radical coexists in three resonant 6. The electron donor substituents make the oxidation
forms. The ortho- and para-phenoxy radicals have a process easier, whereas electron withdrawing substituents
larger spin density, their stability being far higher than the lead to a shift to a higher anodic peak potential.
meta-radical that suffers secondary chemical reactions, 7. As is usual in the electrochemical oxidation of organic
that is, hydroxylation. species, the redox process often involves the participation
4. The presence of an additional electroactive –OH of protons, thus, the higher the pH, the easier the electron
group at the ortho- and para-positions leads to a loss.
two-electron and two-proton pH-dependent reversible
process that, due to higher stability, appears at less The products of mono-phenol oxidation reactions also
positive potentials, than that of the meta-di-phenol or include polymer formation, occurring in an irreversible
mono-phenol. EC mechanism, involving the transfer of one-electron
5. The presence of non-electroactive substituents produces a and one-proton, over the whole pH range. This non-
small oxidation peak potential shift (generally not higher electroactive polymeric film can induce electrode pas-
than 0.20 V); a greater shift occurs when the substituents sivation. The hydroquinone and catechol products of
are linked at the ortho- and para-positions. mono-phenol oxidation (Enache & Oliveira-Brett, 2011b)
1686 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

F I G U R E 8 DPVs baseline subtracted at a

GCE, in 25 μM (a) phenol, (b) catechol, (c)
hydroquinone and (d) resorcinol in pH 7.0, (▬) first
and (•••) second scans, 𝜈 = 5 mV/s. SWVs at a
GCE, in 25 μM (e) catechol and (f) hydroquinone in
pH 7.0, 𝜈 eff = 50 mV/s. Adapted from (Enache &
Oliveira-Brett, 2011b) with permission

undergo further reversible oxidation reactions that occur 2.2 Catechol and hydroquinone moieties
at lower potentials and involve adsorption on the elec- oxidation
trode surface (Janeiro & Oliveira-Brett, 2007; Figures 6
The oxidation of the catechol and hydroquinone di-hydroxyl
and 7).
electron-donating groups follows a reversible two-electron
The phenolates (i.e., the phenolate anions) were described
transfer mechanism, leading to the formation of more
as being easier to be oxidized than phenols, and, for
stable hydroxyl radicals, and at pH 7.0 occurs at very low
pH < pKa , their oxidation is favored, since their formation
positive potentials, at Ep ∼ +0.20 V for catechol, and at
occurs rapidly. A detailed pH-dependent oxidation mecha-
Ep ∼ +0.15 V for hydroquinone (vs. Ag/AgCl, 3 M KCl;
nism of the phenolate anions etoposide and tenoposide, was
Figure 8). The reversibility of the catechol and hydroquinone
reported (Zuman & Holthuis, 2010).
redox processes was confirmed by CV and SWV.
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1687

OH O O explain the higher in vitro antioxidant capacity exhibited by

OH O
natural compounds in which this phenol moiety occurs.
OH
-1e-; -1H+ -1e-; -1H+ The simultaneous detection of hydroquinone and catechol
+1e-; +1H+ +1e-; +1H+ at a boron-doped graphene, in the linear ranges of 5 to
100 μM for hydroquinone and of 1 to 75 μM for catechol, with
detection limits of 0.3 μM for hydroquinone and of 0.2 μM for
OH O O
catechol, was described (Zhang, Sun, Luo, & Wang, 2015).
-1e-; -1H+ -1e-; -1H+
-
+1e ; +1H +
+1e-; +1H+ 2.3 Resorcinol moiety oxidation
The di-phenol resorcinol meta-substitution does not allow
OH OH O
stabilization of intermediates. Thus resorcinol was oxidized
F I G U R E 9 Catechol and hydroquinone oxidation mechanisms. similarly to a mono-phenol at a high positive potential,
Reproduced from (Enache & Oliveira-Brett, 2011b) with permission Ep > +0.7 V (vs. normal hydrogen electrode (NHE)) at
neutral pH (Jørgensen, Madsen, Thomsen, Dragsted, & Skib-
sted, 1999; Jovanovic, Steenken, Hara, & Simic, 1996). The
resorcinol oxidation mechanism occurs in an EC mechanism
The oxidation process reversibility is associated with the that takes place with the transfer of one-electron and one-
stabilization by resonance of the quinonic forms in para- and proton, and the formation of a catechol electroactive product
ortho-substituted di-phenolic compounds (Figure 9), which (Figure 10).
reduces the overpotential. Unlike catechol and hydroquinone reversible oxidation
The catechol and hydroquinone redox reversibility is (Figures 7 and 8), resorcinol undergoes an irreversible
greater in acidic medium, and the electrochemical reaction oxidation process for all pH values (Figure 10a), but the
is pH-dependent over a wide pH range. In very alkaline resorcinol oxidation product oxidizes following a reversible
media (pH > 9.0), the –OH groups suffer deprotonation, redox process (Figure 10b,c).
which causes a pH-independent oxidation that occurs at a Due to its different reactivity, resorcinol presents a higher
lower potential and often involves irreversible bond breaking, oxidation potential than hydroquinone and catechol. Indeed,
dimerization, and a decrease in peak currents (Carvalho, at the meta-position, there is no stabilization of the electro-
Kubota, & Rath, 2003; Fogliatto, Barbosa, & Ferreira, 2010). generated phenoxy radical by resonance. As a rule, para- and
The electrochemical reversible reactions and low oxidation ortho-benzenediol positions oxidize at a lower potential than
potentials of catechol- and hydroquinone-like moieties meta-benzenediol and mono-phenols. The electrochemical

(a) (b)

(c) OH O OH

-1e-; -1H+ -2e-; -2H+

F I G U R E 10 SWVs at a GCE, in 25 μM
resorcinol in pH 7.0, (a) first and (b) second scans, at a +2e-; +2H+
GCE, 𝜈 eff = 50 mV/s, and (c) resorcinol oxidation OH OH OH
mechanism. Adapted from (Enache & Oliveira-Brett,
O OH
2011b) with permission
1688 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

oxidation potential of the simplest phenolic derivatives methyl, can have an important role in driving phenoxy
follows the sequence: radicals’ secondary chemical reactions, such as dimerization
and polymerization that can block a preferential reaction site
hydroquinone < catechol < resorcinol ≤ phenol (Ferreira, Varela, Torresi, & Tremiliosi-Filho, 2006).
Substituents with large Hammett constants shift the phe-
The differences between mono-phenol and resorcinol nolic groups’ oxidation to more positive potentials, whereas
oxidation potentials are usually very small, and they depend electron-donor substituents shift the oxidation to more
on the structural characteristics of the phenolic substituents. negative potentials. Hydrophilic substituents enhance the
The simultaneous electroanalytical detection of hydro- solubility and hydroxyl hydration in aqueous media, and shift
quinone, catechol, and resorcinol, at a GCE modified with the phenolic groups’ oxidation to more negative potentials.
cobalt-iron selenides embedded in porous carbon nanofibers, Conjugated double bonds in phenolic compounds, especially
was achieved, showing a sensor response in the linear ranges double bonds conjugated to the aromatic ring, extend and
of 0.5 to 200 μM for hydroquinone, 0.5 to 190 μM for cate- increase the electron delocalization, improving the phenoxy
chol, and 5 to 350 μM for resorcinol, and detection limits of radical stability and shifting the oxidation to less positive
0.13 μM for hydroquinone, 0.15 μM for catechol, and 1.36 μM potentials.
for resorcinol (Yin, Liu, Bo, & Guo, 2020). Using a composite Non-electroactive substituents may cause electronic and
material consisting of doped graphene into a graphite–ionic steric hindrance effects, which, depending on their size and
liquid n-octyl-pyridinum hexafluorophosphate paste, detec- position relative to the electroactive groups, could signifi-
tion limits of 1.8 μM for hydroquinone, 0.74 μM for catechol, cantly influence the polyphenols’ solubility and diffusion.
and 0.36 μM for resorcinol, in the linear ranges of 10 to In fact, the sugar moieties shift the oxidation peaks to
400 μM for hydroquinone, 10 to 300 μM for catechol, and 1 more positive potentials, with smaller currents (Gil et al.,
to 170 μM for resorcinol, were obtained (Ma & Zhao, 2012). 2013).

2.4 Gallocatechol moiety oxidation

2.6 Effect of electrochemical experimental
Similarly to catechol, the gallocatechol moiety (Figure 2) with conditions
three –OH electron-donating groups, presents a reversible
In electrochemistry, similarly to other techniques, the
oxidation at low potential, associated with a high electron
experimental conditions have great influence. Thus, any
donor capacity, and a voltammetric profile with only small
deduction made from any single voltammogram needs to
differences from catechol (Abdel-Hamid & Newair, 2011;
consider the specific experimental conditions. In fact, the
Gil, Cout, & Couto, 2013).
electrochemical method and the electrode material employed,
In general, the polyphenols’ number of peaks increases
as well as the electrolyte medium, pH, and electroactive
with the number of electroactive groups attached to the
species concentration, directly influence the oxidation peaks’
phenol moiety, and can occur at very close potentials merging
potential, while the temperature and pressure influence is
and changing the expected voltammetric profile. Hence,
negligible (Brett & Oliveira-Brett, 1993, 1998).
due to the small differences among the oxidation potentials
Generally, electrochemical studies of natural phenols are
detected for catechol and gallocatechol, the anodic peaks
performed in a three-electrode cell. The most used working
might overlap. Furthermore, depending on the phenolic
electrode materials are carbon, namely GCE, screen printed
substituents and other experimental conditions, such as pH,
electrodes (SPE), and boron doped diamond electrodes
the electrochemical oxidation of a phenolic compound can
(BDDE), because they have a wide potential window from
show one, two, or more peaks.
–1.0 V to +1.4 V (vs. Ag/AgCl, 3 M KCl), are chemically
inert, impermeable to gases and give reproducible results.
2.5 Effect of substituents on the phenolic
Nevertheless, BDDEs should not be used for potentials
compounds redox behavior
higher than +1.4 V (vs. Ag/AgCl, 3 M KCl), to avoid solvent
The natural polyphenol compounds’ redox behavior is deter- decomposition and formation of •OH radicals that will react
mined by their phenolic electroactive –OH groups present in with the phenolic compounds (Enache, Chiorcea-Paquim,
the molecule, while the phenol group determines the electron Fatibello-Filho, & Oliveira-Brett, 2009).
delocalization and dictates the stability of the radical inter- Inert metal electrodes, such as platinum and gold, are less
mediates, influencing the electrode reaction pathway (Enache used to study the polyphenols’ redox behavior, as they have a
& Oliveira-Brett, 2011a). Other substituents, for example, narrower potential window in aqueous solutions, at positive
methoxyl, acetylesters, glucosides, and keto, may also have potentials, due to platinum and gold oxide formation at
a secondary impact on the voltammetric behavior. Further- ≈+0.8 V (vs. Ag/AgCl, 3 M KCl), and at negative potentials
more, even small non-electroactive substituents, for example, due to interference from oxygen reduction.
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1689

Also, the competing ethanol oxidation for alcoholic 3'

2' 4'
beverages at metal electrodes is less problematic at carbon- O
1' B 5'
8a 8a O 8a O 6'
8 1 1 2 1
based electrodes. Working electrode surface modifications, 7 2 7
8 7 8 2
6 A C3 6 A C3 A C3
by graphene, carbon nanotubes (CNT), carbon paste (CP), 5
4a 4 5
4a 4
6 5
4a 4

carbon composite materials, gold nanoparticles (AuNP), O

magnetic nanoparticles, polypyrrole, Nafion (Naf), chi- Benzopyran Benzopyrone Flavan
tosan, poly-3,4-ethylenedioxythiophene (PEDOT), poly(p- F I G U R E 11 Benzopyran and benzopyrone chemical structures
aminobenzene sulfonic acid) (PABSA), ionic liquids, and
so on, have also been used. Generally, platinum or carbon
auxiliary electrodes, and Ag/AgCl (3 M KCl), NHE or satu- electrodes in aqueous medium induces electrode passivation
rated calomel electrode (SCE) reference electrodes are used. due to formation of a polymer oxidation product, which causes
The experiments are done at room temperature in aqueous a strong decay of the peak currents, while experiments carried
electrochemically inert buffer electrolyte solutions (Perrin & out in the presence of methanol showed an increase of the phe-
Dempsey, 1979), for example, HCl + KCl, citrate, acetate, nol oxidation current (Andreescu, Andreescu, & Sadik, 2003).
phosphate, and ammonia. Nevertheless, due to commonly
low water solubility of polyphenols, mixtures with water of
ethanol or methanol, NaOH, and organic solvents have also 3 FLAVONOIDS AND OT HER
been used. B E N Z O P Y R A N D E R I VAT I V E S
Water-insoluble polyphenols have also been successfully
investigated using solid-state electrochemistry, a proce- The natural compounds containing a benzopyran or a
dure consisting in the mechanical immobilization of solid benzopyrone unit (Figure 11) are largely disseminated
polyphenolic compounds onto the carbon electrode surface in plant tissues. Some very well-known classes of plant
(Janeiro & Oliveira-Brett, 2005; Korotkova, Voronova, & metabolites with this structural pattern include flavonoids,
Dorozhko, 2012). chromones, coumarins, and xantones (Figure 3), and a wide
CV and SWV have been used to study the reversibility variety of pharmacological properties has been associated
of the electron transfer processes. The diffusion coefficient with these derivatives.
of the electroactive species is calculated by CV assays at The great majority of benzopyran derivatives are sub-
different scan rates. This also enables concluding if the stituted with a keto group on the pyran ring, and another
process is adsorption or diffusion controlled, by plotting the aromatic ring is a frequent substituent.
peak current (Ip ) versus the scan rate (𝜈 or 𝜈 1/2 , respectively). Among benzopyran derivatives, flavonoids are the most
CV, DPV, and coulometry have been employed to determine frequent polyphenols found in plants. They are essentially
the number of electrons transferred. composed by the flavan unit, with three rings (A, B, and C;
In DPV, at a scan rate of 5 mV/s, the peak width at half Figure 11), which can be linked by three kinds of substituents,
height, W1/2 , is inversely proportional to the number of hydroxyl, methoxyl, and glucosides. More than 4,000 natural
electrons transferred. The peak width at half height for a flavonoids have been discovered.
reversible reaction is given by W1/2 = 3.52RT/nF = 90/n, Flavo comes from the Latin word flavus and means the
where R is the gas constant, F the Faraday constant, and n color found between yellow and red, such as that of honey
the number of electrons transferred, leading to a value of or gold, and flavonoid refers to an aromatic group, with
W1/2 ∼ 90 for one-electron transfer, and W1/2 ∼ 45 mV for heterocyclic pigments that contain oxygen, which are widely
two-electron transfer (Brett & Oliveira-Brett, 1993, 1998). distributed among plants. Dietary sources of flavonoids
Voltammetric techniques are very sensitive, allowing include green leaves, vegetables, fruits, seeds, wine, tea,
determinations at final concentrations from 1 to 25 μM. The coffee, and some types of grains and spices. Due to their
determination of parameters such as the peak potential (Ep ) occurrence in a broad variety of natural foods, their presence
and peak current (Ip ), are used to assess the polyphenols’ in unaltered concentrations can be considered a chemical
redox behavior and related antioxidant and pro-oxidant fingerprint for quality control of natural products and foods.
mechanisms, and applied to identify the most electroactive Flavonoids also possess numerous health benefits,
polyphenol antioxidants. The plot of Ep versus pH is usually including antibacterial, antiviral, antineoplastic, anti-
a straight line up until the pKa , and slope values of ∼59 mV inflammatory, antiallergic, vasodilatory, and cardioprotective
per pH unit indicate electrode reactions that occur with the properties. It has been demonstrated that flavonoids present
transfer of equal numbers of electrons and protons (Brett & protective effects against oral, gastro-intestinal, colorectal,
Oliveira-Brett, 1993, 1998). liver, reproductive, breast, and lung carcinogenesis, and their
The electrolyte medium also strongly influences the mechanisms of action, either as antioxidants or as modulators
polyphenol redox behavior. Phenol oxidation at platinum of cell signaling, are still under investigation.
1690 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

Flavonoids undergo electrochemical oxidation processes,

which are often coupled to homogenous chemical reactions,
O O
and first- and zero-order processes are generally observed,
consistent with the chemical rearrangements following
OH oxidation.
O O The flavonoids’ oxidation products are often associated
Flavones Flavonols with electroactive adsorbed films with reversible electro-
chemical behavior that, after successive voltammograms,
result in electrode passivation. Furthermore, the low peak
O O
potentials observed for flavonoids’ oxidation products oxi-
dation, and the reversibility of their anodic oxidation, is in
OH agreement with the presence, in the molecules of flavonoid
O O oxidation products, of catechol/hydroquinone-like moieties.
Flavanones Flavanonols The flavonoids’ electroactivity and in vitro antioxidant
capacity are mainly determined by the –OH groups’ number
and position on the aromatic rings. The –OH groups in para-
O O and ortho-positions are oxidized at lower potentials than the
–OH groups in the meta-position. Also, the mono-substituted
OH –OH group on the A-ring requires a higher potential to
Flavanols Anthocyanidins and be oxidized than the –OH group on the B-ring (Janeiro,
Anthocyanins Corduneanu, & Oliveira Brett, 2005; Zhang et al., 2011).
O
Therefore, the electron donor ability of flavonoids is higher,
in the flavonoids with a catechol moiety on B-ring, such as
quercetin, quercitrin, rutin, luteolin, morin, and so on. Thus,
O since the deprotonation is easier, the resorcinol moiety on the
B-ring oxidizes at a close, but slightly lower potential, than the
Isoflavonoids
same group on the A-ring. This relevant effect is illustrated
F I G U R E 12 Flavonoids backbone chemical structures in the electrooxidation of morin, a tetrahydroxy flavonoid,
which occurs with the transfer of one-electron and one-proton.
The steric features of each class of phenolic compounds
Depending on their structure, flavonoids can be classified are also expressed by isomeric forms, which can have
in seven major groups (Figure 12): flavones (flavonones), some influence on their physical and chemical proper-
flavonols (flavon-3-ols), flavanones, flavanonols ties, such as flavonoids, isoflavonoids, coumarins (Matos,
(3-hydroxyflavanones), flavanols (flavan-3-ols, which include Janeiro, Santana, Uriarte, & Oliveira-Brett, 2014), and
catechins, gallocatechins, epicatechin, and epicatechin gal- chromones. Although the benzopyran pattern in coumarins
late), anthocyanidins and anthocyanins, and isoflavonoids and in their isomer chromones may not have a significant
(correspond to an isomeric change on the B-ring bond). effect on their redox behavior, the different pattern leads
The antioxidant capacity of flavonoids depends on their to different stability. Since coumarins are lactones, that
chemical structure, redox properties of their –OH phenolic is, unstable esters, they are more labile in non-neutral
groups, and on the structural relationship between the pH solution, thus can easily suffer hydrolysis to produce
different substituents. the corresponding electroactive ortho-hydroxycinnamic
acids.
The importance of the –OH groups’ position on the
3.1 Electrochemical behavior of flavonoids electron transfer mechanism was illustrated correlating the
Studies concerning the flavonoids’ electrochemical oxidation oxidation peak potentials of apigenin and its isomer genistein
are important for the correct evaluation of their redox (Popa & Diculescu, 2013a). Moreover, diastereomization
behavior, antioxidant, and/or pro-oxidant capacity, and other has very little effect on the flavonoids’ electrochemical
redox properties. oxidation. Therefore, catechin and epicatechin show the
The flavonoids’ anodic oxidation mechanism depends on same electrochemical behavior and comparable antioxidant
a number of experimental variables, including applied poten- capacity (Zhang et al., 2011).
tial, electrode material, pH, inert electrolyte, and solvent, as The flavonoids’ steric hindrance effect on the electron
well as on the stability of electrogenerated intermediates, and transfer reactions, due to substituents, causes a decrease
kinetics of coupled proton and electron transfer reactions. in oxidation peak currents. Considering the effect of
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1691

F I G U R E 13 DPVs at a GCE, in 10−5 M quercetin and 10−4 M rutin, in pH ∼ 1.5, 𝜈 = 5 mV/s. Adapted from (Ghica & Oliveira-Brett, 2005;
Oliveira-Brett & Ghica, 2003) with permission

non-electroactive groups, large bulky groups might ster- 3.2 Flavones, flavonols, flavanones,
ically hamper the electrode reactions, and such an effect flavanonols, and isoflavonoids
must also be considered in the phenolic compounds’ redox
Flavones, flavonols, flavanones, and flavanonols are all
behavior.
C4-keto flavonoids (Figure 12). Very good representative
The DPV obtained for quercetin (Oliveira-Brett & Ghica,
examples of C4-keto flavonoids include the therapeutic drugs
2003) showed different peak potentials than rutin, the
quercetin (Neuwirthová, Gál, Smilek, & Urbánková, 2018),
quercetin glycone derivative, which has a non-electroactive
rutin (Sharma, Ali, Ali, Sahni, & Baboota, 2013; Figure 13),
sugar group (Ghica & Oliveira-Brett, 2005; Figure 13).
and diosmin (Russo, Chandradhara, & De Tommasi, 2018),
Although the number of electrons transferred is the same,
as well as other natural antioxidants, which were studied
the rutin and quercetin electron transfer reaction rates are
using electrochemical methods (Table 1).
different.
The flavones apigenin and acacetin were studied at a
The C3–OH group in flavonoids might also improve their
GCE, both showing irreversible, pH-dependent oxidation
hydrosolubility, enhancing the electron transfer reaction,
processes that occurred with the transfer of one-electron and
while the C2 = C3 double bonds might contribute to electron
one-proton, and the formation of two redox products that were
delocalization, allowing stabilization of the phenoxy radical
reversibly oxidized (Popa & Diculescu, 2013b). Apigenin’s
and decreasing the oxidation peak potential. This explains the
first oxidation peak was shifted to more negative potentials
slight positive shift and low oxidation peak potential observed
with increasing concentration, due to apigenin reorientation
for morin (Janeiro & Oliveira-Brett, 2005) and kaempferol
on the GCE surface, in such a way that stacking and lateral
(Lee et al., 2000), both lacking the catechol moiety on the
interactions became more effective, facilitating its oxidation.
B-ring.
An amperometric sensor for apigenin was developed, using
Whereas the C4 keto group exerts dual functions on the
nickel nanoparticles and activated carbon SPEs (Wang, Wei,
flavonoids’ antioxidant capacity, the C3 and/or C5 hydroxyl
Zhang, Wang, & Li, 2017). Electrochemical sensors for the
substituted derivatives have a bidentate metal chelation
detection and quantification of flavonoids, using multi-walled
site, which has a preventive influence on Fenton oxidative
CNT, and the electrochemical behavior of kaempferol and
mediated processes. The C4 keto group decreases the electron
quercetin, were also investigated (Dar, Naikoo, Hassan, &
density of conjugated –OH groups, enhancing their acidity
Shaikh, 2016; Liang et al., 2017).
and reducing their electron donor ability (Yakovleva et al.,
Isoflavonoids are also C4-keto flavonoids, differing from
2007; Yang, Kotani, Arai, & Kusu, 2001).
the flavones, flavonols, flavanones. and flavanonol isomers,
Flavonols are normally oxidized at lower potentials than
by the position in which the B-ring is linked to the C-ring, at
flavones, since the hydrophilic substituents improve the
the C3 instead of the C2 (Figure 12).
solubility, diffusion, and proton donor ability in aqueous
The isoflavonoids are commonly found in legumi-
media (Nijveldt et al., 2001; Rice-Evans et al., 1996).
nous plants. In addition to their antioxidant properties,
Many flavonoids have been characterized electrochemi-
isoflavonoids exhibit hormonal activity, thus acting as
cally and they are described in Table 1.
 1692

TABLE 1 Anodic peak potentials (Ep vs. Ag/AgCl, 3 M KCl), for different substituted flavonoids

FLAVONOIDS Ep 1 /V E p 2 /V pH SUBSTITUENTS REFERENCES

3C 5A 7A 2´ 3´ 4´ 5´
Luteolin 0.40 1.05 4.0 H OH OH H OH OH H (A. Liu et al., 2008; Y. Peng et al.,
2005; Ramešová, Sokolová,
Tarábek, & Degano, 2013; Zhao,
Zhang, Feng, Qi, & Wang, 2011)
Apigenin 0.68/ 0.99 4.3 H OH OH H H OH H (Masek, Zaborski, & Chrzescijanska,
0.82 2011; Popa & Diculescu, 2013b,
O
2013a; Y. Wang et al., 2017)
Orientin 0.25 0.83 7.0 H OH OH O-sugar OH OH O-sugar (Gil, Enache, & Oliveira-Brett, 2012)
O
FLAVONES
O Diosmin 0.70 1.08 4.0 H OH O-sugar H OH OCH3 H (Diculescu, Satana, Gil, &
Oliveira-Brett, 2012; El-Shahawi,
Bashammakh, & El-Mogy, 2006)
O
FLAVANONES* Diosmetin 0.68 1.06 4.0 H OH OH H OH OCH3 H (Diculescu et al., 2012)
Isorhoifolin 0.65 1.10 5.0 H OH O-sugar H H OH H (Diculescu et al., 2012)
Linarin – 1.10 5.0 H OH O-sugar H H OCH3 H (Diculescu et al., 2012)
Chrysin – 1.05 4.0 H OH OH H H H H (Janeiro et al., 2005; Masek et al.,
2011; Mülazımoğlu &
Mülazımoğlu, 2012)
Eriodictyol* 0.25 0.83 7.0 H OH OH H OH OH H (Gil, Enache, et al., 2012)
Hesperitin* 0.52 1.00 7.0 H OH OH H OH OCH3 H (D. Zhang et al., 2011)
Hesperidin* 0.65 – 5.0 H OH O-sugar H OH OCH3 H (Volikakis & Efstathiou, 2000)
Naringenin* 0.71 0.95 7.0 H OH OH H H OH H (D. Zhang et al., 2011)
Naringin* 0.39 – 5.0 H OH O-sugar H H OH H (Pękal, Dróżdż, Biesaga, & Pyrzynska,
2012; Volikakis & Efstathiou, 2000)
(Continues)
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…
TABLE 1 (Continued)

FLAVONOIDS Ep 1 /V E p 2 /V pH SUBSTITUENTS REFERENCES

3C 5A 7A 2´ 3´ 4´ 5´
Myricetin 0.30 – 3.6 OH OH OH H OH OH OH (Uliana, Garbellini, & Yamanaka,
2014; Volikakis & Efstathiou, 2000)
Quercetin 0.20 0.4 7.0 OH OH OH H OH OH H (Dueñas et al., 2010; Kummer, Ruth,
Kühn, & Kragl, 2014; Oliveira-Brett
& Ghica, 2003; Sokolová et al.,
O
2011; Volikakis & Efstathiou, 2000;
D. Zhang et al., 2011)
OH
Rutin 0.40 1.06 4.0 O-sugar OH OH H OH OH H (Blasco et al., 2004; Ghica &
O
FLAVONOLS Oliveira-Brett, 2005; Magarelli,
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

O Lima, Silva, Souza, & Castro, 2014;

Masek et al., 2011; Volikakis &
OH Efstathiou, 2000)
O Quercetrin 0.32 – 5.0 O-sugar OH OH H OH OH H (Adam et al., 2007; Volikakis &
FLAVANONOLS**
Efstathiou, 2000)
Fisetin 0.35 – 5.0 OH H OH H OH OH H (Brondani et al., 2010; Kummer et al.,
2014; Markovic, Mentus, &
Markovic, 2009; Volikakis &
Efstathiou, 2000)
Rhamnetin 0.30 – 4.5 OH OH OCH3 H OH OH H (Volikakis & Efstathiou, 2000)
Isorhamnetin 0.36 1.15 4.0 OH OH OCH3 H OH OH H (Kummer et al., 2014; A. L. Liu et al.,
2008)
Morin 0.44 0.98 4.0 OH OH OH OH H OH H (He, Yuan, Du, Hu, & Wang, 2009;
Janeiro & Oliveira-Brett, 2005;
Kummer et al., 2014; Masek,
Chrzescijanska, & Zaborski, 2014;
Masek et al., 2011; Xiao, Zhou,
Xiao, Zhao, & Zeng, 2006)
Kaempferol 0.45 – 3.6 OH OH OH H H OH H (Kummer et al., 2014; Uliana et al.,
2014; Volikakis & Efstathiou, 2005)
Galangin 0.50 – 5.0 OH OH OH H H H H (Masek et al., 2011; Volikakis &
Efstathiou, 2000)
Robinin 0.75 0.95 7.0 O-sugar OH O-sugar H OH H H (Gil, Enache, et al., 2012)

Taxifolin** 0.39 1.03 4.0 OH OH OH H OH OH H (Janeiro et al., 2005)

(Continues)
1693
 1694

TABLE 1 (Continued)

FLAVONOIDS Ep 1 /V Ep 2 /V pH SUBSTITUENTS REFERENCES

3C 5A 7A 2´ 3´ 4´ 5´
Catechin 0.28 0.61 7.0 OH OH OH H OH OH H (El-Hady & El-Maali, 2007; Janeiro &
Oliveira Brett, 2004; Maoela et al.,
O 2009; D. Zhang et al., 2011)
Epicatechin 0.21 0.60 7.0 OH OH OH H OH OH H (D. Zhang et al., 2011)
OH
FLAVANOLS Epicatechin gallate 0.45 0.87 2.0 gall OH OH H OH OH H (Novak, Seruga, & Komorsky-Lovric,
2009)
Epigallotechin 0.38 0.89 2.0 gall OH OH H OH OH OH (Novak, Šeruga, & Komorsky Lovri,
gallate 2009)
Peonidin 0.35 0.82 4.0 O-sugar OH OH H OCH3 OH H (Janeiro & Oliveira-Brett, 2007)

Petunidin 0.40 0.85 4.5 OH OH OH OCH3 OCH3 OH OCH3 (Janeiro & Oliveira-Brett, 2007)
Malvin 0.49 0.91 4.0 O-sugar O-sugar OH H OCH3 OH OCH3 (Janeiro & Oliveira-Brett, 2007)

Oenin 0.49 0.83 4.0 O-sugar OH OH H OCH3 OH OCH3 (Janeiro & Oliveira-Brett, 2007)

O
Cyanin 0.42 0.91 4.0 O-sugar O-sugar OH H OH OH H (Janeiro & Oliveira-Brett, 2007)

ANTHOCYANINS AND
ANTHOCYANIDINS*** Kuromanin 0.49 0.83 4.0 O-sugar OH OH H OH OH H (Janeiro & Oliveira-Brett, 2007; Lima
et al., 2007)
Delphinidin*** 0.33 0.82 4.0 OH OH OH H OH OH OH (Janeiro & Oliveira-Brett, 2007; Lima
et al., 2007)
Cyanidin*** 0.55 1.10 – OH OH OH H OH OH H (Lima et al., 2007)
Biochanin A – 1.15 4.0 – OH OH H H OCH3 H (Popa & Diculescu, 2013a)
O Genistein 0.72 1.03 4.0 – OH OH H H OH H (Fogliatto et al., 2010; Han et al.,
2009; Popa & Diculescu, 2013a)
Daidzein 0.78 1.00 4.5 – H OH H H OH H (Fernandes et al., 2012; Han et al.,
O
ISOFLAVONOIDS 2009; Y. Peng, Chu, Liu, & Ye,
2004)
Puerarin 0.81 – 4.0 – H OH O-sugar H OH O-sugar (Han et al., 2009; J.-X. Wang et al.,
2012)

sugar = glycoside moiety; gall = gallate residue

PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1695

OH OH OH
OH OH OH

HO O HO O HO O
OH OH

OH OH OH
OH OH OH

(+)-Catechin (+)-Gallocatechi n (-)-Epigallocatechi n

OH OH
OH OH

HO O HO O
OH

O O
OH OH OH OH
O O

OH OH
OH OH
(-)-Epicatechi n Gallate (-)-Epigallocatechin Gallate
F I G U R E 14 Catechin, gallocatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate chemical structures

phytoestrogens in mammals and have been therapeutically similar biological activity and redox behavior. Daidzein is
used to minimize the effects of menopause symptoms. Other reduced to its end metabolite S-equol, a 7-hydroxy-3-(4´-
studies demonstrated that they are useful molecules against hydroxyphenyl)-chroman, which has a chemical structure
proliferation of different types of malignant cancer cells: similar to the mammalian hormone estradiol, and shows
stomach, prostate, neuroblastoma, brain, breast, and so on. beneficial effects on the reduction of menopausal symptoms,
Therefore, isoflavonoids have also been extensively studied, as well as on the incidence of prostate cancer. Therefore,
and the antioxidant properties and redox behavior of some oxidation of the 4′ ,7-isoflavandiol derivative on the C-ring
of the most representative isoflavonoids, that is, genistein, may not have any implication on hormonal activity. The
daidzein, puerarin, and equol have been evaluated using irreversible oxidation of puerarin, the 8-C-glucoside of
electrochemical techniques. daidzein, using a nano-CeO2 CNT-modified GCE, has also
Genistein is the major occurring isoflavonoid in soybeans, been investigated (Chen, Zhang, & Jiannong, 2001).
fava beans, kudzu, and coffee. It has antioxidant, anticancer,
and anthelmintic properties, and estrogenic activity, but can 3.3 Flavanols
also exercise a pro-oxidant activity, leading to the generation
of free radicals, which can even have beneficial effects by Flavanols (flavan-3-ols) (Figure 12) are derivatives of flavans
poisoning topoisomerase II, thus maintaining DNA stability. that use the 2-phenyl-3,4-dihydro-2H-chromen-3-ol skele-
DPVs of genistein at a GCE showed three irreversible, ton, and include catechin, gallocatechin, epigallocatechin,
pH-dependent processes that occurred with the transfer of epicatechin gallate, and epigallocatechin gallate (Figure 14).
one-electron and one-proton from each –OH group, and Catechin is present in many fruits (e.g., apples, blue-
the formation of two electroactive oxidation products that berries, gooseberries, kiwi, strawberries, etc.), green tea,
undergo reversible redox reactions (Popa & Diculescu, red wine, beer, chocolate, cocoa, and so on. The DPV of
2013a). catechin at a GCE (Figure 15) allowed establishing the
The second most omnipresent isoflavonoid in soybeans is relationship between voltammetric behavior and in vitro
daidzein, and has also been extensively studied (Fernandes, antioxidant capacity (Issaad et al., 2017). The oxidation of
Oliveira, Ghalkhani, Shahrokhian, & Oliveira-Brett, 2012). the catechol and/or gallate group at pH 2, occurred at a low
Chemically, daidzein is a 7,4´-dihydroxy-isoflavone, thus oxidation potential, Ep < +0.5 V (vs. Ag/AgCl, 3 M KCl),
having two mono-phenolic moieties. The difference between corresponding to a strong antioxidant capacity. The oxidation
daidzein and genistein is the absence of the 5–OH group in of phenol and/or resorcinol occurred at a more positive
genistein, which leads to a resorcinol moiety on the A-ring, potential, Ep ∼ +0.8 V, and the oxidation of resorcinol oxi-
instead of two mono-phenolic groups. Nevertheless, despite dation products occurred at an even more positive potential,
their structural differences, daidzein and genistein have Ep > +1.0 V (vs. Ag/AgCl, 3 M KCl). The first electron
1696 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

Peak 1 HO
OH s.e. O O

HO
B
O
A C
OH O O
Chromones Styrylchromones
HO
Peak 3 F I G U R E 16 Chromones and styrylchromones chemical structures

higher antioxidant capacity, in agreement with the electronic

Peak 2 and steric effects of methylation and glucosylation also
100 nA
observed for flavones. Thus, the steric hindrance caused by
the introduction of sugar moieties, especially when near to
electroactive phenol groups, leads to a positive shift in the
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 oxidation potential, whereas the electron donor character of

E / V(vs. Ag/AgCl)
methyl can make the oxidation easier. On the other hand,
the methoxylation of the electroactive phenolic groups might
lead to the suppression of the anodic processes.
F I G U R E 15 DPVs at a GCE, in 10 μM catechin in pH = 2.2: A series of anthocyanins and anthocyanidins were elec-
( , ) first scan, ( , ) second scan, and ( ) supporting
trochemically characterized (Table 1). Their redox potentials
electrolyte (s.e.), 𝜈 = 5 mV/s. Reproduced from (Issaad et al., 2017)
were in a good agreement with their radical scavenging
with permission
activity (Lima, Sussuchi, & Giovani, 2007) and substitution
pattern. The higher the number of phenolic groups in the
transfer reaction of catechin is a reversible process over the anthocyanin/anthocyanidin structure, the greater their radical
whole pH range (Janeiro & Oliveira Brett, 2004). scavenging activity (Janeiro & Oliveira-Brett, 2007).
The ortho-methylation of catechol groups in catechin
derivatives was also investigated (Dueñas, González- 3.5 Chromones and coumarins
Manzano, González-Paramás, & Santos-Buelga, 2010).
The in vitro antioxidant capacity is lower than that of the Among the benzopyrone derivatives, chromones and
non-methylated parent compound, where the reaction occurs coumarins, as well as their derivatives styrylchromones
at the catechol on the B-ring. and neoflavonoids, are oxygen-containing heterocyclic
compounds with remarkable biological functions.
Similarly to flavones, flavonols, flavanones, flavanonols,
3.4 Anthocyanins and anthocyanidins
and isoflavonoids (Figure 12), chromones also have a
Although anthocyanins (glycones) and anthocyanidins (agly- C4-keto substituted benzopyran C-ring structure, differing
cones) lack the keto group at the C-ring (Figure 12), both have by the absence of the aromatic B-ring directly linked to the
been always included in the large class of the benzopyrone- C-ring (Figure 16). Furthermore, many chromones are
like flavonoids. They are red-blue plant pigments, and are phenylpropanoids, whereas their rarest derivatives,
generally present in the outer cell layers of red fruits (e.g., styrylchromones, have a phenylpropene substituent.
red grapes, blackberry, acai, raspberry, etc.), black rice, red Natural chromones with important antitumor, anti-
cabbage, black beans, and so on. In fact, the antioxidant hepatotoxic, antioxidant, anti-inflammatory, anti-
capacity of these pigmented fruits is strongly related with the spasmolytic, estrogenic, and antibacterial activities have
presence of anthocyanins and anthocyanidins. Not only the driven the continuous search for new natural and synthetic
color, but also the antioxidant activity of such phenolic com- derivatives and, more recently, the study of their antioxidant
pounds is influenced by pH changes, being optimum in the properties and redox behavior by voltammetric techniques.
5.0 < pH < 7.4 range. Metal chelation at the phenolic groups, The electrochemical behavior of different
may also play a major role at physiological pH. In the pres- 2-styrylchromones was studied by CV, and the results
ence of ROS, anthocyanins and anthocyanidins are quickly showed a good correlation with their radical scavenging
oxidized, acting as efficient free radical scavengers, in agree- activity toward ROS and reactive nitrogen species (RNS),
ment with their very low oxidation potential (Amorini et al., a general indication of antioxidant activity. Similarly to
2001). flavonoids, the styrylchromones, which contain a catechol
The presence of catechol or gallocatechol substituent B-ring, have a lower anodic peak potential, meaning a higher
moieties, in anthocyanins and anthocyanidins, leads to a antioxidant capacity (Gomes et al., 2008).
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1697

OH OH O activity, there are few electrochemical studies of coumarins

O (Wang & Liu, 2009; Wu & Dewald, 2001).
OH
Electrochemical data on the redox behavior of 10 new
O OH O synthetic 3-arylcoumarins showed that all coumarins can
O be oxidized at relatively low potentials. The number of
OH
electrons participating in the redox processes was directly
dependent on the number and position of the –OH groups.
Flemichin D Eriosematin A The oxidation of coumarin was irreversible, and it was easier
to oxidize the –OH group at the C8 position than the –OH
F I G U R E 17 Chromone-like flemichin D and eriosematin A
group at the C4’ position. The electrochemical mechanisms
chemical structures
were studied at different pH, providing valuable insights into
their antioxidant activity (Janeiro, Matos, Santana, Uriarte,
& Oliveira-Brett, 2013).
The chromone-like natural polyphenols flemichin D and Ellagic acid (Figure 18a), a phenolic compound derived
eriosematin A (Figure 17), both containing three isolated from ellagitannins, in which two coumarin rings are
phenolic groups, were investigated for their antioxidant condensed, is another strong natural phenol antioxidant com-
capacity and redox properties, using electrochemical and monly found in red fruits, walnuts, and numerous vegetables.
biochemical methods. Flemichin D undergoes anodic oxida- The ellagic acid redox behavior has been extensively studied
tion at lower potentials than eriosematin A (Huang, Gao, & by electrochemical methods, its oxidation being characterized
Hageman, 2004). by the catechol moiety reversible redox reaction at a low
Coumarins and their derivatives neoflavonoids have potential (Cuartero et al., 2011; Komorsky-Lovrić & Novak,
a 2H-chromen-2-one structure, in which the keto group 2011).
exists at the C2 position, thus differing from their isomers, The rare neoflavonoids are coumarin analogues, also being
chromones, and flavonoids (Figure 18a). The coumarin struc- considered flavonoids, since the aromatic B-ring is con-
ture is biochemically derived from ortho-hydroxycinnamic nected directly to the benzopyrone C-ring at the C4 position
acid (ortho-coumaric acid) via lactonization, the resulting (Figure 12). Nevertheless, up to this moment, neoflavonoids
lactone being hydrolyzed, especially at acidic pH, in this have not been studied by electrochemical methods.
way regenerating the corresponding cinammic acid pre-
cursor (Figure 18b). Nevertheless, both forms coexist at
6.8 < pH < 11.2. Among their main characteristics is
3.6 Xanthones
that they are both commonly recognized by their fragrant
properties. Xanthones are natural products chemically related to
Coumarins are widespread in many plants, mainly in flavonoids, consisting of two benzene rings bridged through
sweet-smelling plants such as tonka bean (Dipteryx odorata), a carbonyl group and oxygen (Figure 19). Each ring is
vanilla grass (Anthoxanthum odoratum), sweet woodruff connected in a fused and planar structure, thus preventing
(Galium odoratum), mullein (Verbascum spp.), sweet grass free rotation around the carbon–carbon bonds.
(Hierochloe odorata), cassia cinnamon (Cinnamomum Xanthones are typically polysubstituted, and occur as
aromaticum), and sweet clover (Fabaceae spp.), in which either fully aromatized, dihydro-, tetrahydro-, or, more rarely,
the fragrance and bitter taste may cause a repulsing effect on hexahydroderivatives. They are subdivided into six groups:
herbivorous. More than 300 coumarins have been isolated xanthones, xanthone glycosides, prenylated xanthones, xan-
and identified, umbelliferone, esculetin, and scopoletin thonolignoids, bisxanthones, and miscellaneous xanthones.
(Figure 17) being related respectively to p-coumaric, caffeic, Nevertheless, only a few hundred xanthones have been
and ferulic acids, some of the most widespread coumarins in identified, a number far lower than the number of flavonoids.
nature. Xanthones’ unique backbone structure, along with the
Coumarins are widely used as precursor molecules in the type and position of attached chemical groups, define their
synthesis of a number of synthetic drugs, especially those that specific functionalities and properties (Figure 19). Xanthones
show effects on reducing edema, like warfarin, which acts and their derivatives possess antioxidant, anti-bacterial, anti-
as a vitamin K antagonist. Besides the therapeutic actions inflammatory, and anticancer activities, and interact with a
on the circulatory system as anticoagulant, antithrombotic, diverse range of biomolecules; they are electroactive, and
and antiplatelet agents, hydroxycoumarins are potent radi- extremely powerful antioxidants. Examples of xanthones are
cal scavengers, while some ortho-hydroxy derivatives can mangostin and mangiferin (Figure 19), which are abundantly
interact with free iron ions, thus exerting Fenton reactions and found in the pericarp of the fruit mangosteen (Garcinia
pro-oxidant activity. However, despite their inherent redox mangostana) and mangoes.
1698 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

(a) OH F I G U R E 18 (a) Coumarin, neoflavonoid and

O O O O HO O O ellagic acid chemical structures, and (b) equilibrium of
coumarin and ortho-coumaric acid

Coumarin
O O OH
7-OH = Umbilliferone OH
6,7-di-OH = Aesculetin
6-OCH3, 7-OH = Scopoletin Neoflavonoid Ellagic acid

(b) O O - OH
OH

COOH

Coumarin Ortho-coumaric acid

(Lactone form) (Coumaric form)

Mangiferin, with ortho 2,3-di-hydroxy and meta 5,7-di- O

1
hydroxy groups, undergoes electrochemical oxidation below
+0.6 V (vs. Ag/AgCl, 3 M KCl) at mild acid pH, and showed
good antioxidant activity in biochemical assays, that is, lipid
O
and albumin oxidative inhibition, which is consistent with
Xanthones
the electron donor ability of catechol-like compounds (Born
et al., 1996; Tchieno, Njanja, Tapondjou, & Tonle, 2014). A Mangiferin: 2,3,5,7-tetra-OH, 6-glucoside
Mangostin: 3,6,8-tri-OH, 2-OCH3,1,7-di-CH2CHC(CH3)2
significant increase in voltammetric sensitivity was achieved
using an ionic liquid–graphene nanosheet paste modified F I G U R E 19 Xanthones chemical structure
electrode (Tajik, Taher, & Beitollahi, 2014).
derivatives exhibit not only flavor properties, for example,
ethyl esters in the essential oil cinnamon, but also high
4 P H E NO L I C AC I D S A N D E ST E R antioxidant capacity and interesting redox behavior (Simic
D E R I VAT I V E S et al., 2007; Sousa, Rocha, Cardoso, Silva, & Zanoni, 2004).
Among hydroxycinnamic acids, caffeic, ferulic, sinnapic,
Together with flavonoids, phenolic acids represent one of the and p-coumaric acids (Figure 20) are perhaps the best
most important and abundant class of non-flavonoid natural representative compounds of this important subclass of
antioxidants, including the hydroxycinnamic (coumaric) natural phenolic compounds, and they have been studied in
and hydroxybenzoic acid derivatives (Figure 20). The different experimental conditions. Moreover, caffeic acid is
hydroxycinnamic acids’ esterification reaction with organic the chemical precursor of many hydroxycinnamic acids and
molecules gives rise to a large number of ester derivatives, ester derivatives, as well as other phenolic compounds, which
for example, hydroxycinnamoyltartaric esters. They can be include coumarins (e.g., aesculetin, scopoletin), and phenolic
found in a variety of matrices, such as grapes and wine, green alcohols (e.g., coniferyl, sinapyl), being also an important
coffee beans and coffee, spices, blueberries, and so on. intermediate in lignin biosynthesis.
Phenolic acids, for example, gallic acid, caffeic acid, Low concentrations of ferulic acid at a gold electrode
rosmarinic acid, and other phenolic acid derivatives, are were investigated by CV, showing the occurrence of one
very powerful natural antioxidants. Similarly to flavonoids, irreversible oxidation peak (Trabelsi, Tahar, Trabelsi, &
in phenolic acids, stronger antioxidant capacity is achieved Abdelhedi, 2005). Caffeic, sinapic, ferulic, and p-coumaric
with increasing the number of –OH groups attached to the acids’ oxidation was investigated by CV at a GCE, at
aromatic ring. mild acid pH (Janeiro, Novak, Seruga, & Oliveira-Brett,
2007; Manaia, Diculescu, Gil, & Oliveira-Brett, 2012). The
experiments showed the strongest antiradical capacity for
4.1 Hydroxycinnamic acids compounds possessing the catechol moiety, such as caffeic
The hydroxycinnamic acids (coumaric acids) are plant acid. The peak potentials, Ep (vs. Ag/AgCl, 3 M KCl),
metabolites, and similarly to flavonoids, their biosynthesis followed the sequence: caffeic acid (Ep = +0.31 V) < sin-
is part of the shikimic acid route. Hydroxycinnamic acid napic acid (Ep = +0.45 V) < ferulic acid (Ep = +0.53 V) <
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1699

R2 O R2 O
R3 R3
OR1 OR1

R4 R6 R4 R6
R5 R5
Hydroxycinnamic acids Hydroxybenzoic acids
Caffeic acid: Salicilic acid:
R1, R2, R5, R6 = H; R3, R4 = OH R1, R3, R4, R5, R6 = H; R2= OH
Ferullic acid: Protocatechuic acid:
R1, R2, R5, R6 = H; R3 = OCH3; R4 = OH R1, R2, R5, R6 = H; R3,R4= OH
Sinapic acid: Gentisic:
R1, R2, R6 = H; R3,R5= OCH3; R4 = OH R1, R4, R6 = H; R2, R5 = OH
p-Coumaric acid: Gallic acid:
R1, R2, R3, R5, R6 = H; R4 = OH R1, R2, R6 = H; R3, R4, R5 = OH
Syringic acid:
Hydroxycinnamoyltartaric esters
R1, R2, R6 = H; R3, R5= OCH3; R4= OH
(R1 = Tartaric acid) Vanillic acid:
Caftaric acid: R1, R2, R5, R6 = H; R3= OCH3; R4= OH
R2, R5, R6 = H; R3, R4 = OH
Fertaric acid:
R2, R5, R6 = H; R3 = OCH3; R4 = OH
Coutaric acid:
R2, R3, R5, R6 = H; R4 = OH

F I G U R E 20 Phenolic acids chemical structures

p-coumaric acid (Ep = +0.73 V), which is in full agreement reaction with tartaric acid that forms hydroxycinnamoyl-
with the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH• ) tartaric ester derivatives (Figure 20). Caftaric, fertaric, and
spectrophotometric method quantification that measures the coutaric acids are naturally occurring hydroxycinnamoyl
radical scavenging effect (Sousa et al., 2004). esters, derived respectively from caffeic, ferullic, and
Electrochemical studies performed with several coumaric acids, and can be found mainly in grapes and wine.
hydroxycinnamic acids (Blasco, Gonzalez, & Escarpa, The additional hydroxyl and the two carboxylic groups of
2004), showed that their redox behavior is mainly a function the tartaric moiety may improve the ester hydrosolubility
of the phenolic electroactive moieties, while the double and chelation properties. Consequently, the conjugation
bond extension, the methoxyl and other non-electroactive between organic compounds, with highly hydroxylated units,
groups might play an important role on the electrochemical is a metabolic pathway that will alter their bioavailability,
profile and antioxidant activity. In amide derivatives, the N enhancing their solubility in cytosolic medium.
atom has been shown to drive secondary reactions, that is, Besides tartaric acid esters, other hydroxylated phy-
derivatizations at the electrode surface, and further chemical tochemicals, such as the glycosides verbascoside (ester
reactions are enhanced when the experiments are carried of caffeic acid and hydroxytyrosol) and chlorogenic acid
out with concentrations of electroactive species greater than (ester of caffeic acid and cyclitol) and other caffeic acid
0.02 mM (Trabelsi et al., 2005). esters, such as rosmarinic acid (caffeic acid ester of 3-(3,4-
The positive effect of the C2=C3 double bond conjugation dihydroxyphenyl)lactic acid) and chicoric acid (derivative of
on electron delocalization, decreasing the oxidation peak both caffeic and tartaric acids; Figure 21) can be involved in
potential (Tsimogiannis & Oreopoulou, 2004) and enhancing the conjugated metabolic reactions.
the electrogenerated radical formation, was also observed for Verbascoside (Figure 21), a relevant hydroxycinnamic acid
hydroxycinnamic acid derivatives. Comparing caffeic acid ester derivative, consists of a central 𝛽-(D)-glucopyranoside
with protocatechuic acid, a slight shift to a higher oxidation unit in which two phenolic units, one corresponding to caffeic
peak potential was observed (Simic et al., 2007). acid and the other to hydroxytyrosol, are linked. Because
of the presence of two similar, but not identical catechol
moieties, verbascoside exhibits an interesting redox behavior,
4.2 Hydroxycinnamoyl ester derivatives
where each of the two-electron two-proton transfer processes
Hydroxycinnamate salts can be formed with inorganic occur at very close potentials, the experimental conditions
cations, and the hydroxycinnamic acid biosynthesis gives being crucial in order to prevent the merging of the reversible
rise to a variety of hydroxycinnamoyl ester derivatives. A processes (Gil, Enache, & Oliveira-Brett, 2013). On the other
particular case is the hydroxycinnamic acid esterification hand, due to the reversibility and the low oxidation potential,
1700 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

OH
OH

OH HO O
O
O O
O HO
O
HO H
O O
HO
O O
HO HO

HO OH OH

OH
Verbacoside Rosmarinic acid

O
HO OH
HO O OH
O O
HO O HO
O OH O OH
O OH
HO O OH HO

Chicoric acid Chlorogenic acid

F I G U R E 21 Verbascoside, and rosmarinic, chicoric, and chlorogenic acids chemical structures

verbascoside possesses a remarkable electron donor ability, acid also has two identical catechol units, the expected
which is translated into powerful antioxidant properties. The voltammetric profile will exhibit a single reversible process.
presence of the sugar unit increases its aqueous solubility and Chlorogenic acid is an ester of caffeic acid and quinic
bioavailability; therefore, verbascoside has also been used as acid (Figure 21), being the major phenolic compound in
an anti-aging active compound in cosmetic formulations. coffee. The electrochemical oxidation of chlorogenic acid, at
Rosmarinic acid, the aromatic spice Rosmarinus officinalis Ep = +0.38 V (vs. Ag/AgCl), showed a peak potential higher
principal phenolic compound, is an ester derivative formed then caffeic acid, at Ep = +0.31 V (vs. Ag/AgCl), by CV at
by two catechol-containing phenolic acids, the caffeic acid, a GCE in mild acid pH (Teixeira, Gaspar, Garrido, Garrido,
and the 3,4-dihydroxyphenyl lactic acid (Figure 21), and the & Borges, 2013).
similarities of the electron density over each catechol moiety
are high (Gonçalves, Battistin, Pauletti, Rota, & Serafini, 4.3 Hydroxybenzoic acids
2009). Similarly to verbascoside, the redox mechanism of
rosmarinic acid is due to catechol groups’ oxidation. There- The family of hydroxybenzoic acids (Figure 20) occurs nat-
fore, rosmarinic acid is reversibly oxidized in two consecutive urally in plants, and is perhaps, together with some essential
pH-dependent oxidation steps, the first corresponding to the oils, the simplest class of natural antioxidants. Examples
caffeic acid moiety oxidation, and the second corresponding of powerful hydroxybenzoic acid antioxidants include
to oxidation of the 3,4-dihydroxyphenyl lactic acid residue. protocatechuic, vanillic, syringic, gentisic, salicylic, and
Each step is consistent with a two-electron two-proton gallic acids. Hydroxybenzoic acids’ antioxidant capacity
process. is correlated with the substituent number and position,
Chicoric acid, a di-caffeic ester derivative, with two gallocatechol and catechol substituents conferring the highest
hydroxycinnamic units linked through a tartaric acid residue antioxidant capacity.
(Figure 21), is a hydrosoluble natural antioxidant, which has Hydroxybenzoic acids are capable of scavenging free
called the scientific community’s attention due to its immuno- radicals, thus protecting important biological molecules, for
logical action, especially as an HIV virus inhibitor. However, example, DNA, proteins, and phospholipids, and of restoring
despite the very good hydrosolubility and high redox activity small physiological antioxidant agents, such as ascorbic
of the chicoric acid electroactive groups, electrochemical acid, tocopherol, and glutathione. They also exhibit good
research has been very scarce. Therefore, since chicoric chelation properties, which are greater in ortho-hydroxy
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1701

analogues, such as salicylic acid, since the –OH moiety out (Radovan et al., 2008), and the electrochemical oxidation
at this position provides an alternative bidentate site for of each similar catechol unit was evaluated. The parabens’
metal binding. Furthermore, these derivatives generally electrochemical oxidation behavior, at a BDDE, both in
present a low redox potential, high electron donor ability, hydro-alcoholic and aqueous media, has been investigated
and pharmacophoric group interaction with cyclooxygenases (Gil, Andrade, Barbosa, Braga, & Serrano, 2012).
(Kilmartin, 2003).
Since the hydroxybenzoic acids’ radical scavenging
and metal chelation activities are dynamic processes, the 5 Q U I NO N E S
relatively small size of such class of natural phenolic antiox-
idants improves their diffusion properties, which may have a Natural or synthetic quinones present biological and phar-
positive influence on their overall antioxidant capacity. In macological activity, some being tested for their antitumor
turn, non-electroactive electron donor substituents increase activity. Among natural quinones, the naphthoquinones, a bi-
the electron spin density on the phenolic moiety, thus cyclic system with a C6-C4 skeleton, and the anthraquinones,
enhancing their reducing power. a tri-cyclic system with a C6-C2-C6 skeleton (Figure 22), are
Hydroxybenzoic acids and their ester derivatives also perhaps the most representative.
exhibit well established antimicrobial activity, low concen- Naphthoquinones and anthraquinones are plant secondary
trations being extensively used as preservatives in foods, metabolites often described as chromatic pigments, and,
cosmetics, and pharmaceuticals, and higher concentrations despite other important biological functions, they have
as topical active antifungal compounds. Good examples of been mostly used as natural dyes and as building blocks of
hydroxybenzoic acid preservatives are salicylic acid (ortho- synthetic dyes.
hydroxybenzoic acid), and a large diversity of parabens The quinone moiety is intrinsically electroactive, under-
(para-hydroxybenzoic acid ester derivatives). going, at a low potential, a reversible two-electron transfer
The redox behavior of salicylic acid, at GCE and BDDE, is process (Enache & Oliveira-Brett, 2011b), and influencing
pH-dependent and the number of electrons transferred is dif- the redox behavior of all natural naphthoquinones and
ferent from the number of protons (Enache, Fatibello-Filho, anthraquinones (Grygar, Kučková, Hradil, & Hradilová,
& Oliveira-Brett, 2010). The oxidation of 2-(hydroxyl)-4- 2003).
(trifluoromethyl)-benzoic acid, a synthetic trifluoromethyl
substituted salicylic acid, showed the influence of the –CF3
substituent on the aromatic ring.
5.1 Naphthoquinones
The salicylic acid oxidation process was compared with Naphthoquinones are present in many natural compounds,
those of meta-hydroxybenzoic acid, para-hydroxybenzoic most of them possessing significant pharmacological prop-
acid, and a number of flavonoids and hydroxycinnamic acids, erties. Good examples of naphthoquinones include lapachol,
using CV (Simic et al., 2007). The presence of several –OH phylloquinone (vitamin K), juglone, lawsone, and plumbagin
substituents was important and determinant for the free (Figure 22). Plants with naphthoquinone content have been
radical scavenging capacity and electrochemical behavior, extensively used in traditional medicine to treat malignant
and electron donor substituents at the para-position enhanced and parasitic diseases. Besides the vitamin function, some
the electron density of the phenol moiety, thus making the derivatives have shown significant anti-inflammatory and
anodic process easier. antipyretic properties, as well as diverse cytotoxic actions
Gallic acid (3,4,5-tri-hidroxybenzoic acid) and its deriva- expressed by antibacterial, antifungal, antiviral, and insec-
tives are abundant in different types of fruits and plants, ticidal activities. For this reason, the naphthoquinones are
including grapes, and in wine, being important natural archetypes of many medicinal drugs.
antioxidant compounds. Gallic acid was extensively studied The electrochemical behavior of juglone and plumba-
by electrochemical methods, using different electrode mate- gin (Figure 22) is a function of the chemical stability of
rials (Abbasi, Daneshfar, Hamdghadareh, & Farmany, 2011; electrogenerated radical anions, and was evaluated by elec-
Blasco et al., 2004; Ghoreishi, Behpour, Khayatkashani, trochemical and spectroelectrochemical methods (Manaia
& Motaghedifard, 2011; Khan, Ahmad, & Hadi, 2000; et al., 2012). A good correlation between juglone and
Kilmartin, 2003; Zheng & Wang, 2001). Gallic acid possess plumbagin redox behavior and cytotoxic properties was
a catechol moiety and has a low oxidation potential, Ep = observed (Hernández-Muñoz, Gómez, González, González,
+ 0.26 V (vs. Ag/AgCl), at a GCE in pH 7.0, present- & Frontana, 2009). Besides the influence of pH, the solvent
ing a strong in vitro antioxidant capacity (Hernanz-Vila, chosen also has big impact on the electrochemical behavior of
Jara-Palacios, Escudero-Gilete, & Heredia, 2017). naphthoquinones.
The redox behavior of hydroxybenzoic acid ester deriva- Arylnaphthoquinone derivatives with the –OH group
tives, belonging to the chemical class of parabens, was carried at position C3, have a higher electron donor ability, and
1702 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

O O O

1
O
8 8 1 8 9 1
7 2 7 2 7 2
6
6
5 4
3 6
5 4
3 5 10 4 3

O O
1,4-Naphthoquinones 1,2-Naphthoquinones Anthraquinones
Juglone: 5-OH Lapachol: 2-OH, 3-(3-methylbut-2-enyl) Chrysazin: 1,8-di-OH
Lawsone: 2-OH Rhein: 4,5-di-OH, 2-COOH
Plumbagin: 2-CH3, 5-OH Physcion: 1,8-di-OH, 3-OCH3, 6-CH3
Vitamin K: 2-CH3, Emodin: 1,3,8-tri-OH, 6-CH3
3-[(E)-3,7,11,15-tetramethylhexadec-2-enyl]

F I G U R E 22 Naphthoquinones and anthraquinones chemical structures

are easier to oxidize, at Ep ∼ +0.18 V (vs. Ag/AgCl, 3 M transfer pathway from the reduced hydroxyanthraquinones
KCl), at pH 7.4, showing that both their redox potential to dioxygen species, was shown to be directly connected
and antioxidant capacity are influenced by their substituents to the redox activity and electron donor properties of each
(Wurglics, Michelitsch, & Wurm, 2002). anthraquinone (Su, Wang, & Chen, 2006).
DPVs of emodin in the presence of DNA showed that the
5.2 Anthraquinones emodin oxidation peak shifted to a more positive potential
and the peak current decreased with increasing DNA concen-
Anthraquinones, also called anthracenediones or dioxoan- tration; emodin intercalation into the DNA double helix was
thracenes, are natural pigments responsible for the color proposed (Su et al., 2006).
of many plants, fungi, lichens, and some insects, being Considering that the anthraquinone cytotoxic activity
recognized for their organoleptic properties, that is, bitter is mediated by DNA interactions (Al-Otaibi et al., 2017;
taste and intense color. They can be found as aglycone or gly- Oliveira-Brett et al., 2002), the use of DNA modified GCE is a
cosides, characterized by the presence of one or more sugar promising investigation tool to study the anthraquinone–DNA
molecules linked to their tricyclic ring (Figure 22). Some interaction.
important anthraquinones found in nature include emodin
from Rhamnus spp., aloe-emodin and rhein from Rrehum and
Cassia spp., and chrysazin from Cassia spp and Senna spp.
Anthraquinones have been known for their purgative 6 LIGNINS
effects, and more recently as anticancer drugs that exhibit
cytotoxic activity through interaction with DNA and inhi- Lignins are complex biopolymers, which are often related to
bition of topoisomerase II activity (Al-Otaibi, Spittle, & the structural backbone constitution of plants. They bind the
Gogary, 2017; Oliveira-Brett, Vivan, Fernandes, & Piedade, cells, fibers and vessels, and are one of the main constituents
2002). of wood; in fact, the name lignin derives from the Latin word
The electrochemical oxidation of chrysazin and carminic lignum, which means wood.
acid (Figure 22) was investigated at a GCE (Gil, Oliveira, Lignin presents a complex and heterogeneous struc-
& Oliveira-Brett, 2012). Chrysazin oxidation processes ture with a non-defined monomeric pattern, for example,
are associated with the tautomeric forms of the quinoidal organosolv, Figure 23, is very resistant to degradation, being
moiety obtained by its di-hydro tautomer form, followed by held together by strong chemical bonds, and many internal
the oxidation of the 1–OH and/or 8–OH groups. Carminic H-bonds. Its remarkable cation exchange properties improve
acid oxidation occurs in a cascade mechanism, first in the the overall plant activity, including photosynthesis. Since
electron-donating groups, the hydroquinone and the catechol lignin is one of the most stable phytochemical classes, and
moieties, followed by oxidation of the 3–OH group. exhibits a very slow decomposition rate on soil, lignin
The electrochemical behavior of aloe-emodin, a variety of biosynthesis has an important role in carbon sequestering.
emodin present in aloe latex (Figure 22), was investigated at a This polymer family is one of the major renewable,
modified GCE, and showed two well-defined redox processes non-fossil sources of aromatic and cyclohexyl compounds,
(Bian, Zhang, Xiong, Zhang, & Wang, 2010). Cathodic elec- which can be delivered in water, thus altering its organoleptic
trochemiluminescence (ECL) of emodin, rhein, and physcion properties. In fact, the organoleptic impact of lignin related
(Figure 22) showed that the ECL of the formed lucigenin was compounds is not exclusive to water, but also to all types of
enhanced in proportion to the anthraquinone concentration. beverages. Therefore, many lignin studies are concerned with
Furthermore, the reaction mechanism involving an electron remediation processes.
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1703

OH
O OH
OH

HO OH
OH O
OH OH
HO
OH HO O
O O OH
O OH
O O O
O O O
O OH
OH O O O
O
OH HO O O
O O O OH
HO
O OH OH
O HO O O
HO
O O O O
O HO OH
OH O O
O
O

O OH
HO
Organosolv O OH HO
O
OH
HO OH
OH
F I G U R E 23 Lignin organosolv chemical structure HO
OH

Tannic acid
The cork from the cork oak tree Quercus subber, used
F I G U R E 24 Tannic acid (tannin, gallotannic acid) chemical
to produce wine bottle stoppers, can undergo deterioration,
structure
releasing chemicals that alter the wine flavor. The contami-
nation known as “yellow spot” has called the wine industry’s
attention. A wine model matrix, in contact with cork samples habit of growth, but can also be extracted from seaweeds.
contaminated by “yellow spot,” showed the occurrence of an The most often observed property of tannins is their affinity
oxidation process at +0.58 V (Ag/AgCl, 3 M KCl), attributed to bind with proteins, starches, cellulose, and minerals. The
to lignin phenolic compounds’ oxidation, and indicated this compounds belonging to this class are often described as
as a possible biomarker of lignin degradation (Rocha, Ganito, bitter, puckery, drying, and astringent, due to their ability
Barros, Carapuça, & Delgadillo, 2005). of forming insoluble complexes with salivary proteins, and,
In order to obtain a fingerprint of the functional groups therefore, enabling their role in plant protection, by deterring
within the lignin molecule, abrasive stripping voltammetry the animals from eating them. Tannins also provide color,
was used. Lignin and four lignin model compounds were flavor, and structure to red wine and act as a preservative.
investigated (Chen, Rogers, & Compton, 2010), in different Often, wines with heavy tannins are meant to be cellared
solvents, including ionic liquids, neutral, acid, and alkaline for some time, a process during which the tannins tend to
electrolytes, as well as using two different types of elec- mellow out while enhancing the wine’s body and flavor.
trodes, gold macrodisk, and BDDE that allowed a wider Tannins are compounds with medium to high molecular
electrochemical potential window. weight, between 500 and 3,000 Da, and are often divided
Since lignins have a polyphenolic structure they have into two main groups: hydrolysable and condensed tan-
antioxidant properties, and, besides the free phenolic groups, nins. Hydrolysable tannins consist of a central glucose
the ortho-methoxy groups, and the double bonds between molecule linked to molecules of gallic acid (gallotannins) or
the outermost carbon atoms in the side chain, also lead to hexahydroxydiphenic acid (ellagitannins). The most common
an increase in scavenger activity. The lignins’ molecular hydrolysable tannin is tannic acid (also called tannin or gal-
weight and 𝜋-polyconjugation systems play an important lotannic acid; Figure 24). Condensed tannins are polymeric
catalyst/activator role in their radical scavenging activity. flavans that are not readily hydrolysable, which often consist
However, the lignin polymeric structure heterogeneity of catechin and epicatechin building units.
was shown to decrease the antioxidant capacity of lignin All tannins present remarkable antioxidant and radical
derivatives (Dizhbite, Telysheva, Jurkjane, & Viesturs, 2004). scavenging properties, which have been extensively studied
by electrochemical methods, showing redox potentials similar
to those of simple phenolic compounds (Hagerman et al.,
7 TA N N I N S 1998).
Many electrochemical studies for the quantitative deter-
Tannins are naturally occurring complex phenolic com- mination of tannins have been undertaken. An example
pounds found in many plants, particularly those with a woody is the determination of tannic acid, using different types
1704 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

of CP modified electrodes as a sensor device (Xu et al., eugenol–sesamol mixtures, where the antioxidant capacity
2009). The voltammetric behavior of tannic acid on a was increased by 28.5% (Palma et al., 2017).
CNT-modified GCE (Wan, Zou, Yan, Zhao, & Zeng, Cordigol and cordigone (Figure 25b) present
2007), showed an adsorption controlled oxidation at Ep = oxidation potentials varying between +0.45 V
+ 0.42 V (vs. SCE), involving the transfer of one electron and +0.80 V (vs. Ag/AgCl, 3 M KCl), by CV, and their
and one proton. antioxidant properties were compared using two different
The antioxidative properties of ferulic, sinapic, tannic biochemical antioxidant assays, AAPH (2,2′ -Azobis(2-
acids, and malvin, their co-pigment with an anthocyanin methylpropionamidine) dihydrochloride)-mediated oxidation
molecule, were electrochemically investigated by CV of serum albumin, and lipid peroxidation (Born et al.,
(Marković, Ignjatović, Marković, & Baranac, 2003). The 1996).
oxidation potentials were used as a quantitative parameter to The flavonolignans silybin (also named silybinin;
assess the compounds’ in vitro oxidation capabilities, and the Figure 25b), isosilybin, silydianin, and silycristin are impor-
following sequence of increasing in vitro antioxidant capacity tant components of silymarin, a standardized extract from
was observed: the seeds of the milk thistle Silybum marianum, which
possesses recognized antioxidant properties. The antioxidant
ferulic acid < sinapic acid < tannic acid. properties and redox behavior of silybin, its derivatives (2,3-
dehydrosilybin, 7-O-methylsilybin, and 20-O-methylsilybin)
The in vitro antioxidant capacity of malvin co-pigments and isosilybin were evaluated and compared taking into
with these acids was greater in pH 3.6 than in pH 2.5 buffer account their chemical structure. At mild acid pH, silybin
solutions, and the co-pigment malvin-ferulic acid was oxi- and its derivatives oxidize at a low potential, at Ep ∼ +0.5 V
dized more easily than the malvin co-pigments with organic (vs. Ag/AgCl, 3 M KCl), confirming that they are relatively
acid. strong antioxidants (Zatloukalová et al., 2011, 2013). In
fact, silybin and 2,3-dehydrosilybin are capable of chelating
transition metals, especially Cu (II), and the silybin/Cu
8 LIGNANS complex together with hydrogen peroxide cause DNA
damage, evidencing in vitro antioxidant and pro-oxidant
Lignans are secondary plant metabolites produced by oxida- capabilities.
tive coupling of two phenylpropanoid units (Figure 25a).
They are found in many plants, where they play a key role
in plant development and defense against pathogens, having
important pharmacological properties, which include antitu- 9 ST I L B E N E S , C U RC U M I NOI D S ,
mor, anti-inflammatory, immunosuppressive, cardiovascular, AND CHALCONES
antioxidant, and antiviral actions.
Although the lignan skeleton consists of only two Stilbenes, chalcones and curcuminoids are natural phenolic
phenylpropane units (Figure 25a), the molecular backbone compounds found in various plant species, characterized
presents an enormous structural diversity, that leads to by two phenolic rings linked by an alkyl chain, that also
different families, in which furofurans (e.g., pinoresinol), present an extraordinary antioxidant capacity, as well
2,6-diarylfurofurans (e.g., sesamin and sesamolin, and as estrogenic, antibacterial, antifungal, antiviral anti-
sesamol, the thermally degraded product of sesamolin), allergic, anti-inflammatory, and anti-cardiovascular disease
tetrahydrofuran derivatives (e.g., cordigone), furobenzopyran properties.
derivatives (e.g., cordigol), flavonolignans (e.g., silybin), and Stilbenes, also known as stilbenoids, are stress metabolites,
aryltetrahydronaphthalenes (e.g., podophyllotoxin), are a few produced in response to fungal infection. The stilbene class
examples (Figure 25b). includes resveratrol, pterostilbene, gnetol, piceatannol, with
Sesame has been extensively used as a traditional health the phenyl rings linked by a two-carbon ethene bridge.
food, while sesame oil is considered an important ingredient Resveratrol (Figure 27) is the most representative stilbene,
in Ayurvedic medicine in India, and is used in Chinese being an organic metabolite that can coexist as two isomers,
medicine to increase energy and prevent aging. Raw sesame trans- and cis-resveratrol, being present in different plant
seeds are rich in sesamin and sesamolin lignans, also fruits, including grapes and blueberries. The antioxidant
presenting trace amounts of sesamol. The interdependent capacity of trans- and cis-resveratrol has been evaluated
cooperative and competitive response of mixtures of eugenol, by CV, DP, and SWV, at a GCE and different pH values.
thymol, sesamol, and limonene, and their antioxidant capac- The resveratrol redox behavior is characterized by two
ity were measured by DPV at an Hg electrode (vs. Ag/AgCl, irreversible, adsorption controlled, pH-dependent processes,
3 M KCl), and a large cooperative effect was obtained in one due to the phenol group oxidation, and the other due
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1705

(a)

Phenylpropanoid unit Lignan structure

(b)
O H O
O
O O O
O
OH
OH O H
O
O O

Pinoresinol Sesamolin
OH
HO OH
HO
O
O
OH
O
O

HO O OH
HO O
HO
OH
OH OH

Cordigone Cordigol
O
OH O H
HO O
OH OH
H
O
O
HO O O

O O
O
O O
OH
Silybin Podophyllotoxin
F I G U R E 25 (a) Phenylpropanoid unit and lignan structure, and (b) examples of lignans chemical structures

to the resorcinol moiety oxidation (Airado-Rodríguez, induce apoptosis in tumor cells. Phlorizdin’s redox behavior
Galeano-Díaz, & Durán-Merás, 2010; Corduneanu, Janeiro, was investigated by DPV at a GCE, showing that its oxidation
& Oliveira-Brett, 2006). occurs at higher potentials, Ep = +0.53 V (vs. Ag/AgCl, 3 M
Chalcones are open chain flavonoids in which the two KCl), than cinnamic acids, flavanols, and flavonols (Blasco
aromatic rings are joined by an aliphatic three-carbon 𝛼,𝛽- et al., 2004). An electrochemical sensor for phlorizdin detec-
unsaturated carbonyl system. They are similar to flavonoids, tion, using SWV at a BDDE, was also developed (Mehmeti,
being important for plants’ defense against pathogens and Stanković, Ortner, Zavašnik, & Kalcher, 2017).
insects, and for the flower pigmentation to attract pollinators. Curcuminoids are natural phenolic compounds derived
Chalcones have important therapeutic properties, that is, from turmeric (Curcuma longa) root, which is a member
antioxidant, antimicrobial, cytotoxic, anticancer, antipro- of the ginger family (Zingiberaceae), and their biological
tozoal, antiulcer, antihistaminic, and anti-inflammatory properties have been extensively investigated. The main
activities. Synthetic compounds based on the chalcone curcuminoid found in turmeric is curcumin, with a cen-
skeleton, with different pharmacological properties, have tral seven carbon chain (Figure 26), and being associated
been developed. to numerous health benefits, including against cancer,
Phloretin (Figure 27) presents a potent antioxidant capacity by regulating tumor suppressor pathways and triggering
in peroxynitrite scavenging and inhibition of lipid peroxida- mitochondrial-mediated death in tumor tissue, Alzheimer’s
tion. The chalcone phlorizdin, a glucoside of phloretin, also disease, Parkinson’s disease, heart failure, diabetes, and
presents many biological functions, including antioxidant arthritis. Curcumin redox behavior was studied using CV,
capacity, regulation of glucose transport, and the ability to DPV and SWV at a GCE (Manaia et al., 2012). The curcumin
1706 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

redox behavior in acidic and mild alkaline media occurs in Vanillin is mainly found in vanilla, whereas eugenol is found
two steps, the first one irreversible, leading to the formation in clove, cinnamon, myrrh, nutmeg, basil, and bay leaf.
of a catechol moiety, and the second one reversible, occurring With the aim of establishing an overall ranking of the
at higher potentials; an electrochemical mechanism was in vitro antioxidant capacity of guaiacol, syringol, vanillin,
proposed. eugenol, their derivatives, and other polyphenols, existent in
The antioxidant activities and reaction mechanisms of wood smoke and smoke flavor additives employed in food
curcumin isomers and curcumin synthetic analogues in ROS industry, their anodic peak potentials were studied (Bor-
scavenging were investigated by CV (Barzegar, 2012; Jha, tolomeazzi, Sebastianutto, Toniolo, & Pizzariello, 2007). It
Mishra, Jha, & Surolia, 2015), showing that the two –OH was found that a larger in vitro antioxidant capacity is achieved
groups play an important role. when there is a conjugated double bond at the para-position,
The redox behavior of curcumin and its chemical ana- for example, in eugenol and isoeugenol, which stabilizes the
logues, ferulic acid, capsaicin, and dihydrocapsaicin, was phenoxy radical in the radical scavenging process. These
compared. Ferulic acid and curcumin presented similar elec- compounds’ in vitro antioxidant capacity follows the order:
trochemical oxidation behavior in two steps, while capsaicin
and dihydrocapsaicin oxidation occurred in one step (Manaia dihydroxybenzenes > 2, 6-dimethoxyphenols
et al., 2012).
> 2-methoxyphenols.

10 ESSENTIAL OILS Eugenol is a monoterpene (i.e., is formed by two isoprene

units; (Figure 26) that presents pharmacological properties,
Essential oils are a source of flavor and fragrance of aromatic being used as local anesthetic, biocide, and against diar-
plants, often being used as condiments in foods, as odor rhea, flatulence, and sickness, its electrochemical oxidation
in perfumes and as traditional drugs to treat a wide variety mechanism at Au and Pt electrodes having been investigated
of disorders. The aerial parts of aromatic plants such as (Wang & Chen, 2011).
oregano (Origanum vulgare), mint (Lamiaceae family), Thymol and its isomer carvacrol are isopropyl methyl
lemongrass (Cymbopogon citratus), sage (Salvia officinalis), substituted phenols (Figure 26) that are also classified as
lavender (Lavandula officinalis), and rosemary (Rosmarinus natural monoterpenes, and present strong antimicrobial and
officinalis) have been widely recommended and used due powerful antioxidant properties (Ultee, Slump, Steging, &
to their antiseptic, antipyretic, analgesic, antispasmodic, Smid, 2000). Both compounds have been successfully inves-
anti-inflammatory, and antioxidant properties. tigated by electrochemical methods, and the occurrence of
Essential oils are complex matrices, consisting of many anodic peaks at potentials lower than +0.6 V (vs. Ag/AgCl)
small molecular weight terpenes with repeated isoprene in neutral pH, is in agreement with their good electron donor
(C5 H8 ) units, but aromatic moieties such as phenolic func- ability (Arteaga et al., 2012; Palma, Ruiz Montoya, Arteaga,
tions, can also exist. Among essential oils that contain & Rodríguez Mellado, 2014).
phenolic functions, guaiacol, syringol, vanillin, eugenol, The thymol redox behavior at a multi-walled CNT-
thymol, and carvacrol are perhaps the most relevant examples modified GCE, and the effect of the type and concentration of
(Figure 26). Besides the phenol moiety, methoxy and short different surfactants in the electrode surface modifier compo-
alkyl chains are frequent substituents in these essential oils, sition, were evaluated (Ziyatdinova, Romashkina, Ziganshina,
the alkyl chain being commonly attached to other oxygenated & Budnikov, 2018). The thymol oxidation mechanism is an
functions that is, ether, alcohol, and aldehyde. adsorption controlled, one-electron one-proton process.
Guaiacol, a o-methoxyphenol, and syringol, a 1,3-
dimethoxyphenol (Figure 26), both originate from the pyrol-
ysis of lignin, are the molecules causing the characteristic 1 1 PHENOLIC ANTIOX IDANTS’
wood smoke smell (Díaz-González, Vidal, & Tzanov, 2011). E L E C T ROA NA LYS I S I N NAT U R A L
They present important pharmacological properties, which PRODUCTS
include expectorant, antiseptic, and local anesthetic actions;
in fact, guaiacol has been used for decades as an expectorant Electrochemical methods show excellent sensitivity, selec-
active compound in syrup formulations. Vanillin and eugenol tivity, low detection limits, and huge potential for minia-
(Figure 26) are also relevant essential oils and famous turization, excellent price, and portability, being suitable
flavors, being widely used in the food and pharmaceutical for the quantification of low levels of natural polyphenols
industries. They contain phenol and ether functions: vanillin in natural complex matrices, even in crude samples. The
is para-substituted with an aldehyde group, while eugenol is electroanalytical evaluation of polyphenolic content, in vitro
para-substituted with an unsaturated propylene group. total antioxidant capacity quantification, and HPLC–EC, are
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1707

F I G U R E 26 Phenolic essential oils OH OH

chemical structures R1 O O R1

R2
R2

Guaiacol (R1 = H, R2 = H)
Syringol (R1= OCH3, R2 = H) Thymol (R1 = H, R2 = OH)
Eugenol Carvacrol (R1 = OH, R2 = H)
Vanillin (R1 = H, R2 = CHO)

fundamental for the electrochemical quality control of natural at Ep ∼ +0.40 mV, with gallic acid and/or polyphenols con-
products and foods. taining an ortho-diphenol group, the peak shoulder at Ep ∼
+ 0.47 V, with quercetin glycosides, the peak at Ep ∼ +0.64
V in red wines, with malvidin anthocyanins, and the oxi-
11.1 Electrochemical characterization of
dation peaks above Ep ∼ +0.70 V in white wines, with
crude samples
meta-diphenol and/or isolated phenol groups.
Polyphenols’ voltammetric profile is directly related to their The polyphenols theaflavin, theaflavin-3-gallate,
phenol content. Nevertheless, in the case of crude samples, theaflavin-3′ -gallate, theaflavin-3,3′ -digallate and epi-
usually more than one electroactive species is present, and, gallocatechin gallate, in black tea infusions, were electro-
due to the samples containing polyphenols of different types chemically detected at CNT modified SPEs, in the linear
and different numbers of substituents, additional peaks and range of 0.28 to 94 μM, with a detection limit of 0.11
shoulders occur, depending on the specific experimental μM (Murakami et al., 2019). Their anodic peaks were in
conditions (Pannala, Chan, O’Brien, & Rice-Evans, 2001). theaflavin, at Epa ∼ +0.30 V (vs. Ag/AgCl, 3 M KCl), corre-
Qualitative determinations of phenolic compounds by elec- lated with the catechol group in the benzotropolone ring, and
trochemical methods are based on the identification of each in theaflavin-3-gallate, theaflavin-3′ -gallate, and theaflavin-
electroactive compound in complex natural samples. 3,3′ -digallate, at Epa ∼ +0.35 V (vs. Ag/AgCl, 3 M KCl),
The electroanalytical experimental conditions employed correlated with the catechol groups in the benzotropolone
for quantitative analysis of natural phenolic compounds ring and the pyrogallol group in the gallate ring.
present in food and folk and/or traditional medicines, are The electroanalytical determination of ellagic acid in the
listed in Table 2. presence of flavonols, such as quercetin and kaempferol, in
Wine is one of the major sources of polyphenols in the complex matrices of strawberries, raspberries, and blackber-
diet, therefore, the electroanalyitical determination of wine ries was achieved, and the ellagic acid oxidation peak was
polyphenols has been extensively studied (Arribas et al., observed, at Ep = +0.28 V (vs. Ag/AgCl, 3 M KCl), the
2012). Polyphenols in diluted solutions of red and white current being proportional to the ellagic acid concentration
wines were quantified by CV and DPV at carbon electrodes, within the interval 0.5 to 8.0 μM (Komorsky-Lovrić &
and presented good linear relationships (Kilmartin, Zou, Novak, 2011).
& Waterhouse, 2002; Rodrigues, Gomes, Fernandes, & The simultaneous determination of the monoterpenes
Oliveira-Brett, 2019). Several anodic peaks were detected eugenol, thymol and carvacrol in honey samples, by SWV
(Ep vs. Ag/AgCl, 3 M KCl) and were identified: the peak

HO

HO
OH
HO OH HO

cis-Resveratol trans-Resveratol

O O OH O

O O

HO OH HO OH OH
F I G U R E 27 Resveratrol, curcumin and phloretin
chemical structures Curcumim Phloretin
TABLE 2 Electroanalytical methods quantification of natural phenolic compounds in complex matrices
1708

Phenolic Electrochemical Detection

compound Electrode material Electrolyte solution Method/Peak potential Linear range Limit Matrix Reference
2
Aloe-emodin GPNaf-GCE 0.1 M PBS pH 7.0 SWV; 0.6 V 5 nM to 1 μM 2 nM Radix Rhei herbal drugs (Li, Chen, Zhang, Lu, & Yang,
2010)
Aloe-emodin IL-CP THCl pH 1.0 DPV; 0.01 to 12.4 μM 3.0 nM Herbal drugs (Y. Wang, Xiong, Zhang, &
Wang, 2010)
Caffeic acid Pt-RDE B-R pH 1.5 LSV, 0.68 V2 161 to 265 mg/L 385 μg/L Arnica montana tinctures (Reyes-Salas, Rangel-Ordoñez,
Manzanilla-Cano,
Barceló-Quintal, &
Dosal-Gómez, 2002)
Caffeic acid Ppy/Lac/ ABS pH 3.5 Amperometry; –0.45 V1 1 to 250 μM 0.83 μM Propolis (Mohtar et al., 2019).
AuNPs/SPE
Caffeic acid, GCE ABS pH 5.6 LSV 0.1 to 0.8 μM 0.01 μM Orange juice (Sousa et al., 2004)
Chlorogenic
acids
Catechin 𝛽CD-CP 50 mM PBS:BBS pH O-SWV 3.5 to 70.0 μM 1.35 μM Commercial tea (El-Hady & El-Maali, 2007)
7.0
Catechin GCE PBS pH 7.5 SWV; 0.63V1 6.7 to 16.7 ppm 0.84 ppm Ethylacetate extracts of C. (Maoela et al., 2009)
Mellei and C.
Quadrifidus
Catechin pAF-GC PBS pH 6.8 DPV 0.25 30 μM 72 nM. Tea beverages (X.-G. Wang, Li, & Fan, 2010)
Catechin I-GCE pH 3.6 Potentiometric titration 10 to 600 mM 0.6 mM Wine (Castaignède, Durliat, &
Comtat, 2003)
Curcumin dysprosium NW-CP 50 mM PBS pH 4.0 SWV 2 nM to 1 μM 0.5 nM Blood samples; Food (Daneshgar et al., 2009)
industry
Daidzein MWCNT/GCE 0.1 M ABS pH 4 SWV 0.2 to 1.25 μM 80 nM – (Fernandes et al., 2012)
DNA-GCE ABS pH 3.6 DPV, 0.04 to 2 μM 20 nM Ampelopsis (L. Zou, Xu, Luo, Zhang, &
Dihydromyricetin Ye, 2012)
Diosmin GCE B-R pH 3.0 AdS-DPV 0.05 to 9 μM 35 nM Pharmaceutical (El-Shahawi et al., 2006)
Ellagic acid GCE M KNO3 SWV; 0.28 V1 0.5 to 8 μM 135 nM Strawberries, raspberries, (Komorsky-Lovrić & Novak,
pH 6.5 blackberries 2011)

Ellagic acid GCE 0.1 M ABS pH 5.5 SWV; 0.42 V1 0.1 to 1.5 μM 34 nM Fruits; Nuts; Juices (Cuartero et al., 2011)
Emodin CP 0.4 M ammonium buffer - 0.59 V2 0.3 to 40 nM 0.1 nM Polygonum multiflorum (Yan, 2005)
pH 8.2 thumb extract
Emodin GCE 50 mM CV; − 0.235 V2 0.09 to 8 μM 7.8 nM Herbal drugs (L. Wang, Zhang, & Ye, 2006)
ammonium:ethanol
(50%) pH 7.2
(Continues)
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…
TABLE 2 (Continued)
Phenolic Electrochemical Detection
compound Electrode material Electrolyte solution Method/Peak potential Linear range Limit Matrix Reference
Emodin, Rhein, GCE 0.01 M KCl ECL 0.08 to 2 μM; 0.3 to 21, 160, 52 Herbal drugs (Su et al., 2006)
Physcion 8.0 μM; 0.1 to 1.0 nM
μM
Ferulic acid DDAB/N-CP 0.1 M ABS pH 5.5 CV; 0.44 V2 2 to 120 μM 0.4 μM Pharmaceutical (Luo et al., 2010)
formulations
Gallic acid HMD 0.1 M BBS pH 7.5 AdS-CV; − 1.04 V1 0.1 to 600 ng/mL 0.05 ng/mL Tea; urine; plasma blood (Abbasi et al., 2011)
serum
Genistein HMD 0.04 M PBS-MeOH SWV 0.1 to 1.1 μM 34 nM Soy flour, Soy supplement (Fogliatto et al., 2010)
(8:2); 0.2 μM CTAB
pH 7.5
Honokiol; AB-CP 0.1 M PBS pH 6.0 DPV 0.5 to 300 μg/L;10 to 0.94 nM; 18.8 Traditional Chinese (X. Yang, Gao, Hu, & Zhang,
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

Magnolol 250 μg/L nM medicine 2011)

Puerarin CeO2 N/CN/GCE 0.1 M PBS pH 6.0 Amperometry;0.62 V2 0.04 to 6.0 μM 8 nM Pharmaceutical (Ji, Wang, Zhang, & Fang,
formulations 2011)
Quercetin Naf-CN-GCE H2 O:EtOH pH 3.8 O-SWV 0.02 to 2 μM < 0.2 μM Yellow onion (G.-R. Xu & Kim, 2006)
Quercetin CN-CP ABS pH 5.5 AdS-CV 0.1 to 1 μM 30 nM Serum and urine (He, Lin, & Pan, 2005)
Quercetin CN-CP 0.1 M PBS pH 4.0 Chronocoulometry; CV 2 to 100 nM; < 2 nM Hydrolysate product of (Xiao, Zhao, & Zeng, 2007)
0.1 to 20 μM rutin

Quercetin CoON-GCE B-R pH 6.8 Chronocoulometry 0.50 to 330 μM 100 nM Ginkgo leaf tablet; Urine (M. Wang, Zhang, Tong, Xu, &
Yang, 2011)
Quercetin, Rutin CN-CP B-R pH 7.0 DPV 0.05 to 5 μM; 0.5 μM; Quercetin-rutin mixture (Lin, He, & Zha, 2006)
0.10 to 10 μM 0.2 μM

Quercetin; GCE 50 mM ABS pH 5.5 HPLC with amperometric – < 100 nM Onion bulbs (Zielińska, Nagels, & Piskuła,
Quercitine detection; CV 2008)
glucosides
Resveratrol GCE 0.10 M perchloric AdS-SWV; 0.72 V1 5.0 to 35 ng/mL 4.2 ng/mL Wine (Airado-Rodríguez et al., 2010)
medium
Resveratrol CP 1 mM KCl + 0.1 M SWV 10 to 165 nM 2 nM Chinese medicine; Urine (H. Zhang, Xu, & Zheng, 2007)
HNO3 pH 1.0
Rutin CN-CP – DPV 0.2 to 10 μM 34 nM Pharmaceutical (A. C. Oliveira & Mascaro,
2011)
Rutin LF-GCE ABS pH 4.6 SWV 0.5 to 10 nM 0.25 nM Tablets (Tyszczuk, 2009)
Rutin ss-HGC PBS pH 5.0 SWV 4nM to 1 μM 1 nM Tablets (S.-H. Wu et al., 2008)
Rutin DNA-IL-CP B-R pH 3.0 DPV 8 nM to 10 μM 1.3 nM Tablets (J.-X. Wang et al., 2012)
Rutin IL-CP ABS pH 4.0 DPV 5 to 80 nM < 5 nM Buckwheat seeds (Macikova, Halouzka, Hrbac,
Bartak, & Skopalova, 2012)
1709

(Continues)
 1710

TABLE 2 (Continued)
Phenolic Electrochemical Detection
compound Electrode material Electrolyte solution Method/Peak potential Linear range Limit Matrix Reference
Rutin Cu(II)-resin-CP 0.10 M KNO3 :1 μM CV 1 to 8 μM 26.5 nM Pharmaceutical (Garcia Freitas, Medeiros, &
HNO3 pH 6.0 Fatibello-Filho, 2009)
Rutin CN-CP 0.1 M PBS pH 3.5 DPV 48 to 960 μM 33.9 nM Tablets (S. Yang, Qu, Li, Yang, & Liu,
2010)
Rutin CN-CP – SWV 0.08 to 1.4 μM; 50 nM Pharmaceutical (Rezaei, Majidi, Ensafi, &
2.0 to 160.0 μM Karimi-Maleh, 2011)

Rutin PABSA-GCE – SWV 0.25 to 10 μM 100 nM Tablets (X. Chen et al., 2010)
Tannic acid CN-GCE 0.1 M PBS pH 4.0 CV 0.05 to 1 μM 8.0 nM Tea and beer (Wan et al., 2007)
Vanillin GCE aqueous: ethyl SWV 50 to 300 μM 0.16 μM Natural vanilla essence (Hardcastle et al., 2001)
acetoacetate biphasic
system
Vanillin Graphite 0.1 M PBS pH 7.4 SWV 5 to 400 μM 0.4 μM Foodstuffs (Bettazzi et al., 2006)
Vanillin CDA/Au- 0.1 M PBS pH 2.0 Amperometry, 1.0 V2 0.2 to 50 μM 40 nM Vanilla bean; Vanilla tea (D. Zheng, Hu, Gan, Dang, &
AgNP/GCE Hu, 2010)
Vanillin GP-GCE PBS:C6 H8 O7 buffer pH DPV, 0.65V3 0.6 to 48 μM 56 nM Commercial biscuits (J. Peng et al., 2012)
5.0
Reference electrodes: 1 (vs. Ag/AgCl, 3 M KCl); 2 (vs. SCE); 3 (vs. Pt wire);
Electrode materials: Hanging mercury drop electrode (HMDE); multi-walled CNs; CP; GCE; rotating disk electrode (RDE); ionic liquid (IL); Nafion (Naf); acetylene black nanoparticle (AB); graphene (GP); flowerlike Co3 O4
nanoparticles (CoO); Gold nanoparticles (AuNP); ethylenediamine (En); nanowire (NW); poly(p-aminobenzene sulfonic acid) (PABSA); poly-aspartic acid (pAF); lead (LF); single-sided heated graphite cylindrical (ss-HGC),
lysine (L); beta-ciclodextrin modified (𝛽CD); biomimetic sensor (BS); polyphenoloxidase biosensor (PPO-Bios); didodecyldimethylammonium bromide (DDAB); cetyltrimethylammonium bromide (CTAB); poly-vinylpyrrolidone
(PVP), polypyrrole/laccase/gold nanoparticles/carbon SPE (Ppy/Lac/AuNPs/SPE).
Electrolyte solutions: Acetate buffer (ABS); borate buffer (BBS), phosphate buffer (PBS); Britton-Robbinson buffer (B-R). tris-HCl buffer (THCl).
Electrochemical methods: CV; linear sweep voltammetry (LSV); SWV; DPV; adsorptive stripping (AdS); Osteryoung (O); ECL; fast Fourier transform (FFT); reversing (R); sequential injection lab-on-valve (SI-LOV).
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1711

at a GCE, was undertaken (Tonello, Moressi, Robledo, interferents, such as vanillic acid, p-hydroxybenzaldehyde,
D’Eramo, & Marioli, 2016). Caffeic acid determination in and p-hydroxybenzoic acid, was investigated (Bettazzi,
extracts of different propolis samples, in the concentration Palchetti, Sisalli, & Mascini, 2006). Owing to electrode pas-
range of 1 to 250 μM and with a limit of detection of sivation by vanillin adsorption, biphasic sonoelectroanalysis
0.83 μM was also achieved, using an electrochemical biosen- was employed to improve its electroanalytical determination
sor based on a laccase nanocomposite film immobilized on in natural samples of vanilla essence (Hardcastle, Paterson,
a AuNP/polypyrrole modified carbon SPE (Mohtar et al., & Compton, 2001), the method not only enhancing the
2019). linear range and reproducibility, but also facilitating the
The electrochemical behavior at a GCE, of the lignans emulsification and extraction of vanillin from the extract,
pinoresinol (Figure 25b), acetoxypinoresinol, and other phe- thus improving the sensitivity.
nolic compounds isolated from virgin olive oil, was studied, An electrochemical method based on DPV was used for
and the lignans’ redox capacity was correlated with their the quantitative determination of quercetin and kaempferol
antioxidant and pro-oxidant properties (Carrasco-Pancorbo in phytopharmaceutical dosage forms. Linear calibration
et al., 2005). Pinoresinol exhibited a stronger in vitro curves in the range of 10 to 270 μg/mL, and detection
antioxidant capacity, whereas the actoxypinoresinol aceto limits of 0.5 μg/mL for quercetin and 0.1 μg/mL for
group in acetoxypinoresinol hindered the opening of the kaempferol were obtained (Aguilar-Sanchez, Ahuatl-Garcia,
ring, thus weakening the pro-oxidant effect, compared with Davila-Jimenez, Elizalde-Gonzalez, & Guevara-Villa,
pinoresinol. 2005). The electroanalytical determination of eugenol in
The virgin olive oil ortho- and para- substi- a pharmaceutical composition was performed at Au and
tuted mono-phenols were quantified at carbon SPEs Pt electrodes (Wang & Chen, 2011). Rutin determination
(Enache & Oliveira-Brett, 2011b; Enache, Amine, Brett, in pharmaceutical formulations was carried out at a CNT
& Oliveira-Brett, 2013). paste electrode, in the linear range of 0.20 to 9.99 μM and
The redox behavior of sesame oil adsorbed onto a with a detection limit of 0.03 μM (Oliveira & Mascaro,
CP electrode was investigated by CV in acid medium. 2011).
The voltammetric profile evidenced the presence of Electrochemical quantitative determinations of polyphe-
the sesaminol and sesamol electroactive compounds, nols showed excellent concentration versus peak current
and their para-hydroxy groups were oxidized at low linear relationships, and present exceptional sensitivity,
potentials (Shiragami, Kim, & Kusuda, 1994), in agree- selectivity, and reproducibility (Table 2) but they are
ment with sesamol’s and sesame oil’s good antioxidant still poorly represented in the pharmaceutical and food
properties. industry. The main difficulty resides in the complexity
Four lignan and two tocotrienol compounds isolated from of the sample matrices containing different polyphenols,
the hexane extracts of Iryanthera juruensis (myristicaceae) which results in superposition of oxidation peaks, making
fruits, were investigated by CV, and the results were related direct analysis difficult. Moreover, prior to electrochemical
to their in vitro antioxidant capacity (Silva, Pereira, Zanoni, identification and determination of the phenolic com-
& Yoshida, 2001). pounds, natural samples generally need preliminary steps
An adsorptive stripping voltammetry method for the of separation and solvent extraction from the biological
determination and quantification of curcumin at a multi- matrix.
walled CNT-modified pyrolytic graphite electrode was also Quality control assays demand reliable, fast, practical,
developed (Chaisiwamongkhol, Ngamchuea, Batchelor- and low-cost methods, conditions that are fulfilled by the
McAuley, & Compton, 2017). Curcumin adsorption on versatile electroanalytical determinations. The quality con-
the electrode surface followed a Langmuir adsorption trol of natural products requires standardization, and the
isotherm. For application to real samples of turmeric, experimental conditions have a big influence, since the
a one-step sample preparation in ethanol has also been chemical composition of the matrices is variable.
developed. Therefore, taking into account natural products’ huge com-
The electroanalytical determination of vanillin was per- plexity, the application of electroanalysis to the identification
formed at different electrode materials (Apetrei, Apetrei, of specific polyphenols needs to be optimized, considering
Saja, & Rodriguez-Mendez, 2011). Vanillin determination the number of electroactive species and secondary chemical
at graphene film-coated GCE showed improvement of the interactions.
vanillin electrocatalytic oxidation, and vanillin trace levels In fact, preliminary separation steps, such as HPLC,
in complex natural samples, such as biscuits, were detected are required before electrochemical detection. In this way,
(J. Peng, Hou, & Hu, 2012). A disposable electrochemical measurement of the total polyphenol content and of the
sensor for the detection of vanillin in commercial vanilla in vitro antioxidant capacity, taking into consideration the
products was described, and the redox behavior of common cooperative action of all the different individual antioxidant
1712 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

species present in the matrix, can be achieved, enabling

more accurate evaluation of the quality and/or health
beneficial/detrimental effects of natural products and food
samples.

11.2 Phenolic composition evaluation by FIA

and HPLC–EC
The analysis of natural polyphenols in complex matrices,
for example, food, wine, tea, beverages, crude extracts, and
phytopharmaceuticals, frequently involves a preliminary
separation step, commonly achieved by FIA, HPLC, and
capillary electrophoresis. Natural polyphenols are generally
electroactive, so that HPLC–EC has been demonstrated to
be highly selective, and to provide important complementary
information to UV-VIS diode array detector (DAD) or mass
spectrometry (MS) detector, concerning not only the polyphe-
nols’ identity and quantity, but also their physico-chemical
properties, such as redox potential and number of electrons F I G U R E 28 Reverse-phase HPLC–EC obtained for Portuguese
exchanged during the redox reaction (Biesaga & Pyrzynska, casts red grape skin extracts diluted 100 times: (A) Jaen, (B) Tinta
2009; Cortina-Puig, Gallart-Ayala, & Lacorte, 2012; Kilinc, Roriz, (C) Alfrocheiro, (D) Touriga Nacional. Peak identification: (1)
2009; Romani et al., 2000) catechin, (2) myrtillin, (3) kuromanin, (4) petunidin-3-O-glucoside, (5)
In order to achieve the polyphenols’ direct quantitative peonidin-3-O-glucoside, (6) oenin, (7) rutin, (8) myricetin, (8) fisetin.
Adapted from (Novak et al., 2008) with permission
analysis, and to solve the problems caused by the interferents
present in natural samples, selective electrodes (Korbut,
Bučková, Labuda, & Gründler, 2003), FIA coupled systems,
and electrophoresis (Moreno, Arribas, Bermejo, Zapardiel, An analytical procedure for quercetin determination in
& Chicharro, 2011) methodologies were also developed. red wine and human urine, using an automated sequential
The major polyphenols in red and white wines, such as gal- injection lab-on-valve system was designed (Wang et al.,
lic acid and catechin were identified by DPV and HPLC–EC 2012). Using optimal experimental conditions, a linear
(Rodrigues et al., 2019; Šeruga, Novak, & Jakobek, 2011). calibration curve in the range of 0.1 nM to 10 μM, and a low
The anthocyanidins (delphinidin, malvidin, peonidin) and detection limit of 1.3 nM and quantitation limit of 4.3 nM
flavanols (catechin, epigallocatechin gallate) were separated were obtained.
first, and the anthocyanins (kuromanin) and flavonols (rutin, The polyphenol content in the skin of four different types
morin, and quercetin) were separated last. of Portuguese red grapes, Jaen, Tinta Roriz, Alfrocheiro,
The polyphenols present in four Pinot Noir musts, during and Touriga Nacional, by DPV and HPLC–EC at GCE,
an 18-day fermentation period prior to barrel storage, were were quantified. Eleven different flavonoids were identified:
examined by CV and HPLC (H. Zou, Kilmartin, Inglis, & cyanidin-3-O-glucoside (kuromanin), delphinidin-3-O-
Frost, 2002). Various hydroxycinammates that exist in grape glucoside (myrtillin), petunidin-3-O-glucoside, peonidin-
pulp were detected at the early stages of fermentation, while 3-O-glucoside, malvidin-3-O-glucoside (oenin), catechin,
anthocyanins and flavonol glycosides from the skin, and rutin, fisetin, myricetin, morin, and quercetin (Novak,
flavanols from the seeds, were detected near the end of the Janeiro, Seruga, & Oliveira-Brett, 2008; Figure 28). DPV
fermentation process. The appearance of each individual combined with reverse-phase HPLC–EC has also been used
phenolic compound, at the corresponding peak potential, for anthocyanin determination (Janeiro & Oliveira-Brett,
was confirmed by CV that also enabled a semi-quantitative 2007; Koźmiński & Oliveira Brett, 2006; Koźmiński &
measurement of galloyl and catechol groups, in agreement Oliveira-Brett, 2008).
with other total phenol determinations. The polyphenols present in fruit extracts from açai,
The polyphenol composition in Muscatel sweet wines was bacuri, buriti, blackberry, black mulberry, blueberry, juçara,
studied by liquid chromatography associated with DAD, MS, physalis, raspberry, and tamarillo, have been detected by
fluorescence and EC detectors. The electrochemical proper- reverse-phase HPLC–EC, using a wall-jet detector flow cell
ties were used as a complementary method of detection of with a GCE in series with a thin-layer flow cell detector with
resveratrol, piceid, gallic acid, protocatechuic acid, catechin, a BDDE ( Gomes, Ghica, Rodrigues, Gil, & Oliveira-Brett,
and quercetin (Hernanz-Vila et al., 2017). 2016).
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1713

Flavonoid standards and the flavonoid content in apricot,

sour cherry, plum, pomegranate, date, prickly pear (cactus
fruit), and nectarine, by HPLC–EC in series with a DAD,
after an extraction method based on microwave-ultrasound,
were detected (Issaad et al., 2017).
The flavonoid composition of 10 honey and two pollen
samples, from different countries, was analyzed by
HPLC–EC, and the detection of delphinidin chloride,
malvidin chloride, catechin, epigalocatechin gallate, epi-
catechin, and kuromanin chloride was achieved (Issaad,
Fernandes, Enache, Mouats, & Oliveira-Brett, 2019).
Reverse-phase HPLC–EC was used for the separation,
F I G U R E 29 Principle of DPPH• radical scavenging capacity
detection, identification, and quantification of the flavonoids assay. Reproduced from (Teixeira et al., 2013) with permission
present in extracts of Calligonum polygonoides Linnaeus, a
woody shrub grown in desert areas, which possesses numer-
ous therapeutic benefits (Gomes, Fernandes, Shekhawat, natural samples in aqueous, organic or mixed phases, many
Kumbhat, & Oliveira-Brett, 2015). studies have chosen to determine quantitatively the global
Caffeic acid, as well as its ester, chlorogenic acid, and the in vitro antioxidant capacity, where the specific antioxidant
flavonoids luteolin and hyperoside, were determined using equivalent is measured using the integral of the current
capillary electrophoresis with electrochemical detection, in peak observed at a specific peak potential. This practice has
extracts of Lonicera japonica Thumb., an important crude been used in many complex matrices, including wines, teas,
herb frequently used in Chinese medicines (Y. Peng, Liu, & juices, and herbal extracts, whereas the formal potentials are
Ye, 2005). tentatively associated with a specific phenolic compound.
HPLC–EC was used for the quantification of the oil sol- The phenolic compounds’ in vitro total antioxidant
uble carnosic acid, extracted from rosemary, and used as an capacity has been evaluated by spectrophotometric methods:
antioxidant in meat and meat products, in the concentration DPPH• (1,1-diphenyl-2-picrylhydrazine) (Mishra, Ojha,
range of 28.38 to 1027.18 μg/L and with a limit of detection & Chaudhury, 2012; Villaño, Fernández-Pachón, Moyá,
of 1.387 μg/L and a limit of quantification of 2.767 μg/L Troncoso, & García-Parrilla, 2007), ABTS (2,2′ -azino-bis(3-
(Škrinjar et al., 2007). ethylbenzothiazoline-6-sulphonic acid) (Šeruga et al., 2011),
The highest concentrations of dietary lignans are found in and DMPD (N,N-dimethyl-p-phenylendiamine) (Katalinic,
flaxseed (Linum usitatissimum). HPLC–EC was shown to be Milos, Kulisic, & Jukic, 2006).
a good method for rapid and simultaneous detection of the The DPPH• spectrophotometric method takes into consid-
lignans secoisolariciresinol diglucoside, secoisolariciresinol, eration the polyphenol antioxidant interaction with the stable
matairesinol, pinoresinol, lariciresinol, hydroxymatairesinol, DPPH• free radical causing its decolorization (Figure 29).
and isolariciresinol in flaxseeds (Marconi, Calabrò, & The in vitro total antioxidant capacity, the total phenol
Perretti, 2014). concentration, is calculated by the Brand–Williams assay
(Brand-Williams, Cuvelier, & Berset, 1995), and is generally
expressed as “efficient concentration” or EC50 , representing,
11.3 in vitro total antioxidant capacity
relative to the blank control, the amount of antioxidant that
electroanalytical evaluation
can produce 50% of DPPH• decolorization.
The total polyphenol content and in vitro total antioxidant Trolox equivalent antioxidant capacity (TEAC) test, which
capacity also varies between the same natural products from is frequently used as an in vitro standard measurement of
different regions. Nonspecific determinations are a very the polyphenolic compounds’ antioxidant capacity, is based
common practice in the analysis of natural products. Indeed, on reaction with the colored ABTS radical cation with
the terms: “gallic acid equivalent,” “catechin equivalent,” maximum absorption at 734 nm, that decreases in intensity in
“caffeic acid equivalent,” “quercetin equivalent,” “ascorbic the presence of antioxidants. However, measuring the TEAC
acid equivalent,” and “trolox equivalent” are frequently used may be unreliable; thus, the development of hyphenated
to express the total polyphenol content in vegetal foodstuffs and alternative techniques, for improving the reliability and
(Makhotkina & Kilmartin, 2010). accuracy of such determinations, has always been a goal
Due to the natural phenolic compounds’ structural com- (Zielinska & Zielinski, 2010).
plexity and diversity, with more than 8,000 different known The Folin–Ciocalteu (FC) method is based on the polyphe-
compounds, and due to the difficulty of measuring each nols’ oxidation in a basic medium by a mixture of tungstate
antioxidant component separately, and their interactions in and molybdate, leading to the formation of molybdenum ions,
1714 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

also being used for the determination of the total phenolic FC, and FRAP assays, and between the charge transfer in the
content. However, the FC method has the disadvantage that it multiple oxidation steps and the TEAC assay, while the BDE
is not specific for phenols; other antioxidants usually present and IP values showed correlations mainly with the antiox-
in natural samples, such as ascorbic acid, also react with idant capacity measured by the DPPH• assay. Moreover,
the FC reagent, increasing the apparent total polyphenol the total phenolic content and specific polyphenol detection
content. Overestimation of the total polyphenolic content in complex matrices, such as red wines, where most of the
is also possible for DPPH• and TEAC assays (Amorati & phenolic compounds are of different and of an oligomeric
Valgimigli, 2015; Pelle & Compagnone, 2018). nature, showed good correlations between the CV method,
Polyphenols have inherent redox properties, and the reverse-phase HPLC, and the FC assay (De Beer et al., 2004).
polyphenols’ in vitro antioxidant capacity and/or radical Based on the analysis of the voltammetric parameters, an
scavenging activity are driven by their electron/proton donor electrochemical index (EI), which enables the electrochemical
ability. Therefore, the electroanalytical approach can be used determination of the in vitro total antioxidant capacity of nat-
to estimate the phenolic compounds’ in vitro total antioxidant ural products, was established. The EI was defined as the total
capacity, taking into account the polyphenol oxidation peak polyphenol concentration obtained when the complete oxida-
potential and peak current (Blasco, Crevillén, González, & tion of all phenolic compounds takes place at a fixed potential
Escarpa, 2007). (Blasco, Rogerio, González, & Escarpa, 2005; Escarpa,
An oxidation that occurs at low potential and with high González, Blasco, Rogerio, & Hervás, 2007). The EI is
peak current is associated with greater electron donor ability. determined, using DPV, as EI = Ip /Ep , taking into account the
Indeed, phenolic compounds with good in vitro antioxidant oxidation peak current, Ip , and oxidation peak potential, Ep, ,
capacity have a low oxidation potential, Ep < +0.45 V (vs. of each antioxidant species (Lino et al., 2014; Neto, Macêdo,
Ag/AgCl) (Simic et al., 2007). A high Ip value is corre- Oliveira, Ferreira, & Gil, 2017; Neto, Oliveira, Ghedini,
lated with higher reaction rates and/or number of electrons Vaz, & Gil, 2017; Oliveira-Neto et al., 2016; Oliveira et al.,
transferred. In the particular case of flavonoids, compounds 2018).
with lower Ep , such as myricetin, quercetin, rutin, luteolin, A good correlation between the EI and the spectrophoto-
taxifolin, myrtillin, and catechin, have a higher antioxidant metric EC50 assays, using the DDPH• method, was found.
capacity than compounds that lack the catechol moiety on However, since EC50 represents the in vitro total antioxidant
the B-ring, which have higher Ep values (Blasco et al., 2004; concentration necessary to reduce the DPPH• concentration
Nasr et al., 2005). by 50%, the EC50 value is inversely proportional to the EI
The polyphenols’ in vitro antioxidant capacity is strongly value.
influenced by the experimental conditions. In most cases, The EI measured by DPV and the EC50 measured by the
the phenolic group oxidation process involves a one-electron spectrophotometric DDPH• method showed that red wines
one-proton transfer, which occurs for –OH groups more have a higher in vitro total antioxidant capacity than white
easily in low pH solution, and is more difficult in high pH wines, since they show higher polyphenol content (Rodrigues
media. In addition, the polyphenols’ free radical scavenging et al., 2019).
activity and electron donor ability are strongly related with a The in vitro antioxidant capacity and the electrochemical
higher number of –OH substituents and conjugation. mechanism of action of hibalactone, isolated from the roots
A good correlation between the polyphenols’ oxidation of Hydrocotyle umbellata L., a groundcover plant that has
potentials calculated by electrochemical methods (Table 1) been used in folk medicine in Argentina, Brazil, Cuba and
and pulse radiolysis techniques was observed (Jovanovic India, to reduce inflammatory processes, was correlated with
et al., 1996), confirming that catechol B-ring derivatives, the hibalactone’s butyrolactone ring (Oliveira et al., 2017).
such as quercetin, Ep ∼ +0.4 V (vs. NHE), catechin, Ep ∼ The antioxidant properties of seaweed tannins were also
+0.40 V (vs. NHE), and epigalocatechin gallate, Ep ∼ + 0.3 studied by electrochemical methods (Keyrouz et al., 2011).
V (vs. NHE), have a very good antioxidant capacity. The quantitative determination of the total flavonol
The electrochemical properties (Ep values and area content, that is, quercetin, kaempferol, and myricetin, in
under anodic peak) corroborated with structural parameters, samples of wine, tea-infusion and tomato juice was reported
deduced from density functional theory (bond dissociation (Volikakis & Efstathiou, 2005), based on flavonol precon-
enthalpy (BDE) and ionization potential (IP)), of different centration on CP electrodes in the presence of diphenylether
flavonoids, were compared with the antioxidant capacity (Zoulis & Efstathiou, 1996). The total flavonoid concentra-
calculated by four spectrophotometric methods: DPPH• , tion, expressed as quercetin equivalent, was determined in
TEAC, ferric reducing ability of plasma (FRAP), and FC the range of 3 to 60 mg/L, with a detection limit lower than
assays (Zhang et al., 2011). The results showed a good 25 μg/L, and the reproducibility of the measurements was
correlation between the electrochemical charge transfer 3% to 6%. However, the flavonol content separation from
corresponding to the first oxidation peak and the DPPH• , the flavanols, such as catechol, which are generally present
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1715

in high concentrations in wine and tea samples, could be a evaluation of oregano quality, was reported (González, Gil,
challenge, as both flavonols and flavanols have low oxidation Mendoza, & Escarpa, 2011).
potentials (Janeiro & Oliveira Brett, 2004). The in vitro antioxidant capacity of essential oils from five
Electrochemical assays in wine samples showed poisoning mint species, Mentha spicata L., Mentha x gentilis L., Mentha
of the electrode surface, especially critical for carbon SPEs, crispa L., Mentha piperita L., and Mentha x piperita L., at a
which led to abnormally low values of the total polyphenol Pt electrode, measuring the decrease of the oxygen cathodic
content of wines (Rocha, Vilas-Boas, Fontes, Geraldo, & peak current with increasing antioxidant oil concentration,
Bento, 2019). was determined (Gonçalves et al., 2009). A methodology to
The use of GCE, gold and platinum electrodes modified measure the mint essential oils’ capability for Fe(II) chelation
by PEDOT conducting polymer, allowed the separation of was proposed.
polyphenols from ascorbic acid in wine and model wine A direct electron transfer assay based on the redox
solution (Türke, Fischer, Beaumont, & Kilmartin, 2012; properties of metal ions and their interactions with
Zhang, Türke, & Kilmartin, 2017). phenolic compounds has been proposed. The ceric
A CV study of 21 Californian red wines showed that the reducing/antioxidant capacity (CRAC) method, the
in vitro total polyphenol content was dependent on the grape electroanalytical variant of the fluorescence recovery
variety, the particular viticulture and wine-making practices, after photobleaching (FRAP), was developed and applied
rather than on wine age, and the results were compared with to several organic compounds (Ferreira & Avaca, 2008).
reverse-phase HPLC and FC assay (Roginsky et al., 2006). A sequence of in vitro antioxidant capacity of the phenolic
The in vitro total antioxidant capacity, measured by compounds: tannic acid > > quercetin > rutin > gallic acid
EI, and the EC50, measured by DPPH• assay, of several similar to catechin > ascorbic acid > BHA > trolox, using
Mediterranean fruits were compared (Issaad et al., 2017). the CRAC assay, was found.
The EI and EC50 of different fruit extracts were also assessed, Electrochemical DNA biosensors have also been used
blackberry presenting the highest, and physalis the lowest in to determine the antioxidant and pro-oxidant properties
vitro antioxidant capacity (Gomes et al., 2016). of quercetin, rutin, catechin, and epigallocatechin gallate
Acerola (Malpighia emarginata) fruits have high polyphe- (Labuda, Bučková, Heilerová, Šilhár, & Štepánek, 2003).
nol (e.g., rutin) and ascorbic acid content. In order to In the presence of transition metal ions, some flavonoids
evaluate the integrity of acerola frozen and dried products also act as pro-oxidant, by reducing the metal ion and
and to detect possible adulteration, a quality control elec- inducing mutagenic activity, a process by which the highly
troanalytical method based on the DPV determination of oxidizing •OH radical is formed, that is capable of causing
acerola electroactive components, was proposed (Benjamin DNA oxidative damage. Quercetin-induced DNA oxidative
et al., 2015). The EI obtained for the acerola samples was damage, after quercetin interaction with Cu(II), has been
in agreement with the antioxidant capacity measured by observed. The DNA-Cu(II)-quercetin complex was studied
the DPPH• assay. by spectrophotometric and electrochemical methods, and
The oxidation of ascorbic acid, at Ep ∼ 0.20 V (vs. SCE), using a DNA-electrochemical biosensor (Oliveira-Brett
represents a problem for the electrochemical characterization & Diculescu, 2004a, 2004b). The radicals formed during
of polyphenols in fruits and beverages, since the ascorbic quercetin oxidation by Cu(II) caused double-stranded DNA
acid oxidation peak tends to merge with the polyphenol (dsDNA) strand breaks, and the appearance of 8-oxoguanine
oxidation peaks. Indeed, commercial samples of acerola that was detected. The dsDNA oxidative damage occurred over
contained excessive amounts of ascorbic acid as additive, time, suggesting that the quercetin-Cu(II) complex interca-
used to prevent oxidation, have led to the mischaracterization lated and slowly interacted with DNA, causing hydrogen
of the polyphenol content and in vitro antioxidant capacity, bond breaks and oxidative damage.
while samples that did not contain the synthetic ascorbic Conjugation of bioactives and pharmacophores with
acid additive led to well-characterized anodic peaks, corre- lipophilic or hydrophilic moieties can multiply their pos-
sponding to both ascorbic acid and other natural electroactive sibilities to interact with biopolymers and substantially
species of acerola (Benjamin et al., 2015). modify their biological activities. Voltammetric studies of
The in vitro total antioxidant capacities of spices, condi- flavonolignan-DNA interactions showed the remarkable
ments and drugs, containing gallic acid, sesamol, eugenol, binding affinity of flavonolignan homoconjugates to dsDNA
thymol, carvacrol, vanillin, salicylaldehyde, limonene, that did not involve intercalation (Zatloukalová et al., 2016).
geraniol, and 4-hexylresorcinol, by electrochemical and Ten honey and two pollen samples were analyzed from
DPPH• methods, were also determined (Arteaga et al., 2012). the point of view of their in vitro total antioxidant capacity.
An electrochemical study of thymol and carvacrol in DPV, DPPH• spectrophotometric assay and electrophoresis
Mexican oregano (Lippia graveolens), using single-walled studies demonstrated their ability to protect dsDNA from
CNT-modified SPEs, proposing the use of EI for fast oxidative damage by •OH radicals generated in Fenton
1716 PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY…

reactions (Issaad et al., 2019; Marconi et al., 2014). The EI taxifolin, myrtillin, and catechin, have a higher in vitro
and EC50 values obtained were in good agreement, with an antioxidant capacity and are able to neutralize free radicals
inverse correlation, as expected. and restore low molecular weight antioxidants, compared to
Electrochemical methods will become important tools in flavonoids without a catechol moiety.
the pharmaceutical and food industries, due to their excellent Polyphenols’ biological characteristics and mechanisms of
sensitivity, low limit of detection, low cost and huge potential action are not only due to their redox behavior and strong in
for miniaturization, and portability. Applications may include vitro antioxidant capacity. Indeed, many natural polyphenols,
the determination of the total phenolic content and specific for example, chromones, coumarins, and flavonoids, have
polyphenol determination in red wines, where most of the been used as models in food and medicinal chemistry research
phenolic compounds are of a diverse and oligomeric nature. focusing on their diverse range of pharmacological properties.
HPLC coupled with electrochemical detectors has been Electroanalytical methods represent an extremely advanta-
demonstrated to be highly selective, providing complemen- geous methodology to evaluate and identify the composition
tary information to HPLC–DAD–MS, concerning not only of natural phenolic compounds, in particular flavonoids,
the identification and quantification of the electroactive in food products, to quantify in vitro their total antioxidant
phenolic compounds, but also their physico-chemical prop- capacity, and to estimate their protection against dsDNA
erties, such as redox potential and the number of electrons oxidative damage, due to the electroanalytical methods
exchanged during the redox reaction. simplicity, rapidity, and small consumption of samples and
materials.

12 CONC LU SI ON S ACKNOW LEDGMENTS

Phenolic compounds present a common redox behavior, This research was sponsored by FEDER funds through
related to the oxidation of hydroxyl groups, and electroactive the program COMPETE–Programa Operacional Factores
and non-electroactive chemical substituents, linked to the de Competitividade, and by national funds through FCT–
aromatic rings, may also influence their voltammetric profile. Fundação para a Ciência e a Tecnologia—under the project
The electrochemistry of flavonoids is very important, and UID/EMS/00285/2020.
needs to be extensively investigated due to their exceptional
antioxidant properties. Flavonoids’ electrochemical oxidation AU T H O R CO N T R I B U T I O N S
mechanism and in vitro antioxidant capacity vary depending
on the number and position of the hydroxyl and other All authors conducted the literature review, prepared figures
substituents on the aromatic rings, but their electron donor and tables, and finalized the manuscript. More specific con-
ability is mostly determined by the B-ring electrochemistry. tributions were: A.-M. Chiorcea-Paquim electroanalysis in
However, complex natural samples, containing different natural products, T.A. Enache electrochemical mechanisms,
polyphenols, require preliminary steps of separation and E.S. Gil natural phenolic compounds electrochemical studies,
solvent extraction from the biological matrix, prior to the and A.M. Oliveira-Brett flavonoid electrochemistry.
phenolic compounds’ electrochemical identification and
quantification. Due to the fact that polyphenols present in CONFLICTS O F INTEREST
the sample may have similar electroactivity, electrochemical
The authors declare no conflicts of interest.
detection coupled with HPLC is necessary.
Electroanalytical methods are also very important for
measuring the phenolic compounds in vitro total antioxidant NO MENC LATURE
capacity, and to detect different electroactive species at a anodic
low concentrations. The polyphenols’ in vitro antioxidant AB acetylene black nanoparticle
capacity and free radical scavenging activity are both strongly ABS acetate buffer
related with the number of hydroxyl substituents and con- AdS adsorptive stripping
jugation, and are dependent on the oxidation peak potential AuNP gold nanoparticles
and current. As a rule, polyphenols with good antioxidant BBS borate buffer
capacity have low oxidation potentials, whereas those with BDDE boron doped diamond electrode
high oxidation potentials can even act as pro-oxidants, and B-R Britton–Robbinson buffer
a high oxidation peak current is correlated with a higher BS biomimetic sensor
reaction rate and/or number of electrons transferred. c cathodic
Flavonoids with a catechol moiety that oxidize at low C chemical reaction
potentials, such as myricetin, quercetin, rutin, luteolin, CNT carbon nanotubes
PHENOLIC ANTIOXIDANTS ELECTROCHEMISTRY… 1717

CoO flowerlike Co3 O4 nanoparticles Eric De Souza Gil

CTAB cetyltrimethylammonium bromide https://orcid.org/0000-0001-9161-0127
CV cyclic voltammetry Ana Maria Oliveira-Brett
CVs cyclic voltammograms https://orcid.org/0000-0002-6244-0891
DAD diode array detector
DDAB Didodecyldimethylammonium bromide
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